Electrochemical energy storage systems and methods

ABSTRACT

A three-dimensional electrode array for use in electrochemical cells, fuel cells, capacitors, supercapacitors, flow batteries, metal-air batteries and semi-solid batteries.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.13/229,479, filed on Sep. 9, 2011, which claims the benefit of andpriority to U.S. Provisional Application 61/381,400 filed on Sep. 9,2010, U.S. Provisional Application 61/416,193, filed on Nov. 22, 2010,and U.S. Provisional Application 61/467,112 filed on Mar. 24, 2011,which are hereby incorporated by reference in their entireties.

BACKGROUND

Over the last few decades revolutionary advances have been made inelectrochemical storage and conversion devices expanding thecapabilities of these systems in a variety of fields including portableelectronic devices, air and space craft technologies, passenger vehiclesand biomedical instrumentation. Current state of the art electrochemicalstorage and conversion devices have designs and performance attributesthat are specifically engineered to provide compatibility with a diverserange of application requirements and operating environments. Forexample, advanced electrochemical storage systems have been developedspanning the range from high energy density batteries exhibiting verylow self-discharge rates and high discharge reliability for implantedmedical devices to inexpensive, light weight rechargeable batteriesproviding long runtimes for a wide range of portable electronic devicesto high capacity batteries for military and aerospace applicationscapable of providing extremely high discharge rates over short timeperiods.

Despite the development and widespread adoption of this diverse suite ofadvanced electrochemical storage and conversion systems, significantpressure continues to stimulate research to expand the functionality ofthese systems, thereby enabling an even wider range of deviceapplications. Large growth in the demand for high power portableelectronic products, for example, has created enormous interest indeveloping safe, light weight primary and secondary batteries providinghigher energy densities. In addition, the demand for miniaturization inthe field of consumer electronics and instrumentation continues tostimulate research into novel design and material strategies forreducing the sizes, masses and form factors of high performancebatteries. Further, continued development in the fields of electricvehicles and aerospace engineering has also created a need formechanically robust, high reliability, high energy density and highpower density batteries capable of good device performance in a usefulrange of operating environments.

Many recent advances in electrochemical storage and conversiontechnology are directly attributable to discovery and integration of newmaterials for battery components. Lithium battery technology, forexample, continues to rapidly develop, at least in part, due to thediscovery of novel electrode and electrolyte materials for thesesystems. The element lithium has a unique combination of properties thatmake it attractive for use in an electrochemical cell. First, it is thelightest metal in the periodic table having an atomic mass of 6.94 AMU.Second, lithium has a very low electrochemical oxidation/reductionpotential (i.e., −3.045 V vs. NHE (normal hydrogen referenceelectrode)). This unique combination of properties enables lithium basedelectrochemical cells to have very high specific capacities. State ofthe art lithium ion secondary batteries provide excellentcharge-discharge characteristics, and thus, have also been widelyadopted as power sources in portable electronic devices, such ascellular telephones and portable computers. U.S. Pat. Nos. 6,852,446,6,306,540, 6,489,055, and “Lithium Batteries Science and Technology”edited by Gholam-Abbas Nazri and Gianfranceo Pistoia, Kluer AcademicPublishers, 2004, are directed to lithium and lithium ion batterysystems which are hereby incorporated by reference in their entireties.

Advances in electrode structure and geometry have also recentlydeveloped. For example, U.S. Patent Application Publication US2011/0171518 and International Patent Application publication WO2010/007579 disclose three-dimensional battery structure for solid-statelithium ion batteries. U.S. Pat. No. 7,553,584 and U.S. PatentApplication Publication US 2003/0099884 disclose quasi-three-dimensionalbatteries in which the electrodes are formed as complementarystructures. These structures, however, do not find use with lead-acidcells, fuel cells, capacitors, supercapacitors or metal-air batteries.

SUMMARY

This invention is in the field of energy storage. This invention relatesgenerally to an electrode array for use in energy storage and energygeneration devices.

In a first aspect, provided are three-dimensional electrode arrays. Inan embodiment, a three-dimensional electrode array comprises a pluralityof plate electrodes, wherein each plate electrode includes an array ofapertures, wherein the plate electrodes are arranged in a substantiallyparallel orientation such that the each aperture of an individual plateelectrode is aligned along an alignment axis passing through an apertureof each of all other plate electrodes; and a plurality of rodelectrodes, wherein the plurality of rod electrode are not in physicalcontact with the plurality of plate electrodes and arranged such thateach rod electrode extends a length along an alignment axis passingthrough an aperture of each plate electrode; and wherein a first surfacearea includes a cumulative surface area the plurality of plateelectrodes, wherein a second surface area includes a cumulative surfacearea of each aperture array and wherein a third surface area includes acumulative surface area of each of the plurality of rod electrodes. In aspecific embodiment, the plurality of rod electrodes are not inelectrical contact with the plurality of plate electrodes.

In embodiments, the three-dimensional electrode array is a component ofa device selected from the group consisting of: a primaryelectrochemical cell, a secondary electrochemical cell, a fuel cell, acapacitor, a supercapacitor, a flow battery, a metal-air battery and asemi-solid battery.

Three-dimensional electrode arrays of this aspect include those having avariety of geometries and physical dimensions. Useful three-dimensionalelectrode arrays include those in which a ratio of the second surfacearea to the first surface area is about 2 or is selected over the rangeof 1 to 5. Useful three-dimensional electrode arrays include those inwhich a ratio of the second surface area to the third surface area isabout 2, is selected over the range of 1 to 5 or is selected over therange of 0.2 to 1. Three-dimensional electrode arrays having a ratio ofthe second surface area to the third surface area selected over therange of 1 to 5 are optionally useful for electrochemical cellembodiments. Three-dimensional electrode arrays having a ratio of thesecond surface area to the third surface area selected over the range of0.2 to 1 are optionally useful for flow battery embodiments, fuel cellembodiments and semisolid battery embodiments.

Three-dimensional electrode arrays of this aspect include those havingany orientation. For example, in one embodiment, a three-dimensionalelectrode array is arranged such that the plate electrodes have ahorizontal orientation. In another embodiment, however, athree-dimensional electrode array is arranged such that the plateelectrodes have a vertical orientation. In one embodiment, athree-dimensional electrode array is arranged such that the rodelectrodes have a horizontal orientation. In another embodiment,however, a three-dimensional electrode array is arranged such that therod electrodes have a vertical orientation.

Three-dimensional electrode arrays of this aspect include those havingplate electrodes with a variety of geometries and physical dimensions.Optionally, each plate electrode in a three-dimensional electrode arrayhas identical or substantially identical dimensions. In certainembodiments, however, the dimensions of each plate electrode areindependent. Optionally, each of the plurality of plate electrodes hasone or more lateral dimensions (e.g., length, width) of about 2 cm, orselected over the range of 20 nm to 20 m or selected over the range of 5mm to 1 m. In embodiments, each of the plurality of plate electrodes hasa thickness dimension selected over the range of 20 nm to 5 cm orselected over the range of 200 μm to 5 mm. In embodiments, a distancebetween each of the plurality of plate electrodes is selected over therange of 10 nm to 5 cm or selected over the range of 200 μm to 5 mm. Inembodiments, each aperture in a plate electrode has a diameter or alateral dimension selected over the range of 10 nm to 20 cm or selectedover the range of 3 mm to 2 cm or selected over the range of 1 mm to 2cm. Optionally, each aperture in a plate electrode has identical orsubstantially identical dimensions and/or shapes. Optionally, eachaperture has a lateral dimension more than 2× a lateral dimension of arod electrode. In certain embodiments, however, the dimensions and/orshape of each aperture in a plate electrode are independent. Optionally,the dimensions and/or shape of each aperture of each plate electrode areindependent. Useful aperture shapes include, but are not limited to,square, rectangular, circular and polygonal. As used herein, the termsaperture and hole are used interchangeably.

Three-dimensional electrode arrays of this aspect include those havingrod electrodes with a variety of geometries and physical dimensions.Optionally, each rod electrode in a three-dimensional electrode arrayhas identical or substantially identical dimensions. In certainembodiments, however, the dimensions of each rod electrode areindependent. Optionally, each rod electrode has a circularcross-section. Optionally, each rod electrode has a non-circular orpolygonal cross-section. Useful rod electrode cross-sectional shapesinclude, but are not limited to, square, rectangular, circular andpolygonal. In an embodiment, each of the plurality of rod electrodes hasa length selected over the range of 50 nm to 20 m or selected over therange of 5 mm to 1 m. In embodiments, each of the plurality of rodelectrodes has a diameter or a lateral dimension selected over the rangeof 9 nm to 20 cm or selected over the range of 3 mm to 2 cm or selectedover the range of 1 mm to 2 cm. Optionally, at least one rod electrodecomprises a group of rod electrodes, wherein the group of rod electrodesis arranged such that the group of rod electrodes extends a length alongan alignment axis passing through an aperture of each plate electrode.Optionally, each rod electrode comprises a cylinder.

Three-dimensional electrode arrays of this aspect include thosecomprising any of a variety of materials. Useful electrode materialsinclude those used in primary electrochemical cells, secondaryelectrochemical cells, fuel cells, capacitors and supercapacitors. Inembodiments, each plate electrode in a three-dimensional electrode arrayindependently comprises a material selected from the group consistingof: a metal, a metal alloy, carbon, graphite, graphene, Li, Mn₂O₄, MnO₂,Pb, PbO₂, Na, S, Fe, Zn, Ag, Ni, Sn, Ge, Si, Sb, Bi, NiOOH, Cd, FeS₂,LiCoO₂, LiCoO₂ doped with Mg, LiNiO₂, LiMn₂O₄, LiMnO₂, LiMnO₂ doped withAl, LiFePO₄, doped LiFePO₄ (Mg, Al, Ti, Nb, Ta), amorphous carbon,mescocarbon microbeads, LiAl, Li₉Al₄, Li₃Al, LiZn, LiAg, Li₁₀Ag₃, B,Li₇B₆, Li₁₂Si₇, Li₁₃Si₄, Sn, LiSSn₂, Li₁₃SnS, Li₇Sn₂, Li₂₂SnS, Li₂Sb,Li₃Sb, LiBi, Li₃Bi, SnO₂, SnO, MnO, Mn₃O₄, CoO, NiO, FeO, LiFe₂O₄, TiO₂,LiTi₂O₄, a vanadium oxide, glass doped with a Sn—B—P—O compound,mesocarbon microbeads coated with at least one of poly(o-methoxyanaline,poly(3octylthiophene) and poly(vinylidene fluoride) and any combinationof these. Optionally, each plate electrode in a three-dimensionalelectrode array comprises identical or substantially identicalmaterials. In certain embodiments, however, the materials of two or moreplate electrodes in a three-dimensional electrode array are different.In certain embodiments, electrical communication is established betweeneach of the plurality of plate electrodes. Optionally, a plate electrodecomprises lithium; a lithium alloy such as lithium-aluminum,lithium-tin, lithium-magnesium, lithium-lead, lithium-zinc orlithium-boron; an alkali metal such as Na, K, Rb or Cs; an alkalineearth metals such as Be, Mg, Ca, Sr, Ba or an alloy thereof; Zn or analloy of Zn; or Al or an alloy of Al.

Optionally, a three-dimensional electrode array comprises a component ofa fuel cell. In one embodiment, the three-dimensional electrode arrayfurther comprises a fuel fluid, such as hydrogen gas or a hydrogencontaining gas or a liquid hydrocarbon fuel, positioned in contact withone or more plate electrodes, one or more rod electrodes or both one ormore plate electrodes and one or more rod electrodes. In an embodiment,the three-dimensional electrode array further comprises an oxygencontaining fluid, such as oxygen gas or air, positioned in contact withone or more plate electrodes, one or more rod electrodes or both one ormore plate electrodes and one or more rod electrodes. Optionally, a flowis provided to the fuel fluid, for example, by a pump. Optionally, aflow is provided to the oxygen containing fluid, for example, by a pump.

Optionally, the three-dimensional electrode array comprises a componentof a metal-air battery. In one embodiment, at least one rod electrodecomprises a metal or at least one plate electrodes comprises a metal orboth at least one rod electrode and at least one plate electrodecomprise a metal. In an embodiment, the three-dimensional electrodearray further comprises an oxygen containing fluid, such as oxygen gasor air, positioned in contact with one or more plate electrodes, one ormore rod electrodes or both one or more plate electrodes and one or morerod electrodes. Optionally, a flow is provided to the oxygen containingfluid, for example, by a pump.

In embodiments, each rod electrode in a three-dimensional electrodearray independently comprises a material selected from the groupconsisting of: a metal, a metal alloy, carbon, graphite, graphene, Li,Mn₂O₄, MnO₂, Pb, PbO₂, Na, S, Fe, Zn, Ag, Ni, Sn, Ge, Si, Sb, Bi, NiOOH,Cd, FeS₂, LiCoO₂, LiCoO₂ doped with Mg, LiNiO₂, LiMn₂O₄, LiMnO₂, LiMnO₂doped with Al, LiFePO₄, doped LiFePO₄ (Mg, Al, Ti, Nb, Ta), amorphouscarbon, mescocarbon microbeads, LiAI, Li₉Al₄, Li₃Al, LiZn, LiAg,Li₁₀Ag₃, B, Li₇B₆, Li₁₂Si₇, Li₁₃Si₄, Sn, LiSSn₂, Li₁₃SnS, Li₇Sn₂,Li₂₂SnS, Li₂Sb, Li₃Sb, LiBi, Li₃Bi, SnO₂, SnO, MnO, Mn₃O₄, CoO, NiO,FeO, LiFe₂O₄, TiO₂, LiTi₂O₄, a vanadium oxide, glass doped with aSn—B—P—O compound, mesocarbon microbeads coated with at least one ofpoly(o-methoxyanaline, poly(3octylthiophene) and poly(vinylidenefluoride) and any combination of these. Optionally, each rod electrodein a three-dimensional electrode array comprises identical orsubstantially identical materials. In certain embodiments, however, thematerials of two or more rod electrodes in a three-dimensional electrodearray are different. In embodiments, electrical communication isestablished between each of the plurality of rod electrodes. Optionally,a rod electrode comprises lithium; a lithium alloy such aslithium-aluminum, lithium-tin, lithium-magnesium, lithium-lead,lithium-zinc or lithium-boron; an alkali metal such as Na, K, Rb or Cs;an alkaline earth metals such as Be, Mg, Ca, Sr, Ba or an alloy thereof;Zn or an alloy of Zn; or Al or an alloy of Al.

In an exemplary embodiment, at least one rod electrode comprises acomposite rod electrode. Useful composite rod electrodes include thosecomprising a rod electrode inner core and a rod electrode outer shellsurrounding the rod electrode inner core. Optionally, the rod electrodeinner core and the rod electrode outer shell are separated by a firstdistance, for example, filled with an electrolyte. Optionally, acomposite rod electrode comprises an electrochemical cell. Optionally arod electrode inner core comprises a solid cylinder. Optionally a rodelectrode outer shell comprises a hollow cylinder. In one embodiment,the rod electrode inner core comprises a first electrode material, therod electrode outer shell comprises a second electrode materialdifferent from the first electrode material, and at least one plateelectrode comprises the first electrode material.

In an embodiment, one or more rod electrodes comprise branched rodelectrodes including branched segments extending along a directionperpendicular to an alignment axis passing through an aperture of eachplate electrode. In one embodiment, branched segments of at least twoneighboring rod electrodes extend a full distance between the at leasttwo neighboring rod electrodes, thereby forming a bridge segment betweenthe at least two neighboring rod electrodes. In embodiments, each rodelectrode is coated with an electrolyte, such as a solid electrolyte.

In an exemplary embodiment, at least one plate electrode comprises acomposite plate electrode. Useful composite plate electrodes includethose comprising a plate electrode inner layer and a plate electrodeouter shell surrounding the rod electrode inner layer. Optionally, theplate electrode inner layer and the plate electrode outer shell areseparated by a first distance, for example, filled with an electrolyte.Optionally, a composite plate electrode comprises an electrochemicalcell. In one embodiment, the plate electrode inner layer comprises afirst electrode material, the plate electrode outer shell comprises asecond electrode material different from the first electrode material,and at least one rod electrode comprises the first electrode material.

In embodiments, a three-dimensional electrode array of this aspectcomprises any number of plate electrodes. For example, usefulthree-dimensional electrode arrays include those comprising 5 or more, 6or more, 7 or more, 8 or more, 9 or more or 10 or more plate electrodes.In embodiments, a three-dimensional electrode array of this aspectcomprises any number of rod electrodes. For example, usefulthree-dimensional electrode arrays include those comprising 50 or more,60 or more, 70 or more, 80 or more, 90 or more or 100 or more rodelectrodes.

In embodiments, an electrode array includes an oxygen electrode, forexample useful in a metal-air battery. Optionally, an oxygen electrodeis exposed to ambient air and molecular oxygen is accessed from theambient air. Useful electrodes include composite carbon electrodes, forexample, about 150 micrometer thick, made of graphite powders and abinder such as PVDF on a Ni mesh.

In certain embodiments, the three-dimensional electrode array is acomponent of an electrochemical cell. Useful electrochemical cellsinclude those selected from the group consisting of: a primary cell, asecondary cell, a lead-acid cell, a lithium cell, a lithium ion cell, ametal-air cell, a zinc-carbon cell, an alkaline cell, a nickel-cadmiumcell, a nickel metal hydride cell, a silver oxide cell, a sodium sulfurcell, a solid electrochemical cell or a fluid electrochemical cell.Optionally, a three-dimensional electrode array further comprises anelectrolyte positioned between each of the plurality of plate electrodesand each of the plurality of rod electrodes or around each of theplurality of rod electrodes. In a specific embodiment, the electrolytecomprises a first electrolyte surrounding each of the plurality of plateelectrodes and a second electrolyte surrounding each of the plurality ofrod electrodes. Optionally, the first electrolyte and the secondelectrolyte are different. Optionally, the first electrolyte and thesecond electrolyte are the same. Optionally, the first electrolyte andthe second electrolyte each independently comprise a solid electrolyte.In a specific embodiment, a membrane is positioned between the first andsecond electrolytes. Optionally, the first and second electrolytes areboth liquids. Optionally, an electrolyte is a fluid of variableviscosity, velocity, composition or any combination of these.

In embodiments, the electrolyte includes any of a variety ofelectrolytes, for example useful in primary and secondaryelectrochemical cells. Useful electrolytes include, but are not limitedto: an aqueous solution; an organic solvent; a lithium salt; sulfuricacid; potassium hydroxide; an ionic liquid; a solid electrolyte; apolymer; poly(ethylene oxide); poly(propylene oxide); poly(styrene);poly(imide); poly(amine); poly(acrylonitrile); poly(vinylidenefluoride); methoxyethoxyethyoxy phosphazine; diiodomethane;1,3-diiodopropane; N,N-dimethylformamide; imethypropylene urea; ethylenecarbonate; diethylene carbonate; dimethyl carbonate; propylenecarbonate; a block copolymer lithium electrolyte doped with a lithiumsalt; glass; glass doped with at least one of LiI, LiF, LiCl,Li₂O—B₂O₃—Bi₂O₃, Li₂O—B₂O₃—P₂O₅ and Li₂OB₂O₃; a sol of at least oneoxide of Si, B, P, Ti, Zr, Bb and Bi; a sol of at least one hydroxide ofSi, B, B, Ti, Zr, Pb and Bi; a gel of at least one oxide of Si, B, P,Ti, Zr, Bb and Bi; a gel of at least one hydroxide of Si, B, B, Ti, Zr,Pb and Bi; or any combination of these. Useful polymers further includepolyacryonitrile, poly(vinyl chloride), poly(vinyl sulfone),poly(ethylene glycol diacrylate), poly(vinyidene fluoride),poly(tetrahydrofuran), poly(dioxolane), poly(ethylane oxide),poly(propylene oxide), poly(vinyl pyrrolidinoe) and mixtures thereof.Useful electrolytes further include those comprising LiClO₄, LiBF₄,LiAsF₆, LiCF₃, SO₃, LiPF₆, and LiN(SO₂ CF₃)₂. Optionally, an electrolytecomprises a salt selected from the group of salts consisting ofMg(ClO₄)₂, Zn(ClO₄)₂, LiAlCl₄, and Ca(ClO₄)₂. Optionally, an electrolyteis a solid, for example comprising a material selected from the groupconsisting of phosphorous based glass, oxide based glass, oxide sulfidebased glass, selenide glass, gallium based glass, germanium based glass,sodium and lithium betaalumina, glass ceramic alkali metal ionconductors, and Nasiglass. a polycrystalline ceramic selected from thegroup consisting of LISICON, NASICON, Li_(0.3)La_(0.7) TiO₃ , sodium andlithium beta alumina, LISICON polycrystalline ceramic such as lithiummetal phosphates.

In certain embodiments, the three-dimensional electrode array is acomponent of a capacitor or a supercapacitor. In one embodiment, athree-dimensional electrode array further comprises one or moredielectric materials positioned between each of the plurality of plateelectrodes and each of the one or more rod electrodes or around each ofthe one or more of rod electrodes. Useful dielectric materials include,but are not limited to: a metal oxide, a silicon oxide, a metal nitride,a silicon nitride, and any combination of these. Useful dielectricmaterials, for some embodiments also include carbon, nanocarbon,graphene and/or graphite. Optionally, a dielectric is substituted by asynthetic resin or polypropylene.

For a variety of three-dimensional electrode arrays, embodiments includeone or more current collectors. In a specific embodiment, each of theplurality of plate electrodes comprises a current collector. In aspecific embodiment, each of the plurality of rod electrodes comprises acurrent collector. In a specific embodiment, each of the plurality ofplate electrodes and each of the plurality of rod electrodes comprises acurrent collector.

Optionally, one or more current collectors are positioned in thermalcommunication with a heat sink or a heat source. Current collectorspositioned in thermal communication with a heat sink or a heat sourceare useful, for example, for heating, cooling and/or controlling thetemperature of a three-dimensional electrode array or a devicecomprising a three-dimensional electrode array, such as anelectrochemical cell. In a specific embodiment, each of the plurality ofplate electrodes comprises a current collector positioned in thermalcommunication with a heat sink or a heat source. In a specificembodiment, each of the plurality of rod electrodes comprises a currentcollector positioned in thermal communication with a heat sink or a heatsource. In a specific embodiment, one or more of the plurality of rodelectrodes' current collectors and one or more of the plurality of plateelectrodes' current collectors are positioned in thermal communicationwith a heat sink or a heat source. Useful current collectors includethose comprising a material selected from the group consisting of: ametal, a metal alloy, Cu, Ag, Au, Pt, Pd, Ti, Al and any combination ofthese. Optionally, each current collector comprises and/or isconstructed as a heat pipe. In certain embodiments, each currentcollector is a structural element of the three-dimensional electrodearray or provides structural support to the three-dimensional electrodearray. Optionally, one or more current collectors is under tension.Current collectors positioned under tensions are useful, for example,for providing structural rigidity to a three-dimensional electrodearray. Useful current collectors include those comprising Ni, such as aporous Ni sheet or a Ni screen or a Ni rod or a porous Ni rod.Optionally, a rod electrode comprises a porous rod. Optionally a porousrod electrode comprises a hollow rod electrode with porous walls. Porousrod electrodes are useful, for example, for permitting the passage ofactive materials, such as a gas, air, or a liquid, such as in asemi-solid battery, a flow battery or a fuel cell.

In a specific embodiment, a three-dimensional electrode of this aspectfurther comprises one or more heat transfer rods arranged such that eachheat transfer rod extends a length along an alignment axis passingthrough an aperture of each plate electrode. For example, one or moreheat transfer rods are positioned analogous to a rod electrode in athree-dimensional array. Optionally, at least one of the one or moreheat transfer rods are positioned in thermal communication with a heatsink or a heat source, for example, for heating, cooling and/orcontrolling the temperature of a three-dimensional electrode array or adevice comprising a three-dimensional electrode array. Useful heattransfer rods include, but are not limited to those comprising amaterial selected from the group consisting of: a metal, a metal alloy,Cu, Ag, Au, Pt, Pd, Ti, Al and any combination of these. Optionally,each heat transfer rod independently comprises a metal or a metal alloy.

In certain embodiments, a three-dimensional electrode array of thisaspect further comprises an inert coating on a surface of one or moreapertures, for example on a surface of each aperture. An inert coatingon an aperture is useful, for example, for preventing electrical contactbetween a rod electrode and a plate electrode, for preventing the growthof dendrites on a plate electrode and/or for preventing an oxidationreaction or a reduction reaction from occurring at a plate electrode atpositions covered by the inert coating. Useful inert coatings includethose comprising a material selected from the group consisting of:Teflon, Delrin, Kapton, polytetrafluoroethylene (PTFE), aperfluoroalkoxy (PFA), fluorinated ethylene propylene (FEP) ,polypropylene (PP), polyethylene (PE) and any combination of these.

In certain embodiments, a three-dimensional electrode array of thisaspect further comprises one or more inert spacer elements positioned toprovide a space between each plate electrode, between each rod electrodeor between each plate electrode and each rod electrode. Useful inertspacers include those comprising a material selected from the groupconsisting of: Teflon, Delrin, Kapton, polytetrafluoroethylene (PTFE), aperfluoroalkoxy (PFA), fluorinated ethylene propylene (FEP),polypropylene (PP), polyethylene (PE) and any combination of these.Useful inert spacers further include those comprising a non-conductingmaterial.

Optionally, for a three-dimensional electrode array embodiment, at leastone rod electrode comprises a first cathode material and wherein atleast one rod electrode comprises a second cathode material differentfrom the first cathode material. Optionally, for a three-dimensionalelectrode array embodiment, at least one rod electrode comprises a firstanode material and wherein at least one rod electrode comprises a secondanode material different from the first anode material.

Optionally, for a three-dimensional electrode array embodiment, at leastone plate electrode comprises a first cathode material and wherein atleast one plate electrode comprises a second cathode material differentfrom the first cathode material. Optionally, for a three-dimensionalelectrode array embodiment, at least one plate electrode comprises afirst anode material and wherein at least one plate electrode comprisesa second anode material different from the first anode material.

Optionally, for a three-dimensional electrode array embodiment, one ormore plate electrodes have a rectangular geometry, a square geometry, anellipsoidal geometry or a circular geometry. Optionally, for athree-dimensional electrode array embodiment one or more rod electrodeshave a diameter or a lateral dimension that changes over a length of arod electrode or linearly increases or decreases over a length of a rodelectrode. Optionally, for a three-dimensional electrode arrayembodiment, each aperture has a diameter or a lateral dimension thatdiffers on each plate electrode, changes along a length of a rodelectrode, or linearly increases or decreases along a length of a rodelectrode.

Optionally, one or more of the plurality of rod electrodes has twodifferent diameters or lateral dimensions, a first diameter or lateraldimension positioned at a region of the rod electrode adjacent to anaperture in a plate electrode, and a second diameter or lateraldimension positioned at a region of the rod electrode at regions betweenplate electrodes, as an example it can be thinner in the vicinity of thewalls of the holes and thicker in the vicinity of the space between theplates.

Optionally, a space between one or more of the plate electrodes acts asa buffer, especially when the plate active material has a significantshape change such as in Si anodes in Li-ion batteries.

Optionally, in a three-dimensional electrode array embodiment, a spacebetween the plate electrodes is filled with oil or water or a heattransfer fluid or a heat transfer solid positioned in thermalcommunication with a thermostat, thereby maintaining the temperature ofthe three-dimensional electrode array at a specified temperature.

Optionally, a three dimensional electrode array further comprises aplurality of inert material gaskets, PTFE gaskets or silicone gaskets,wherein the oil or water or heat transfer liquid or heat transfer solidis separated from an electrolyte between the rods and the hole-walls bythe inert material gaskets, PTFE gaskets or silicone gaskets and whereinthe inert material gaskets, PTFE gaskets or silicone gaskets have ashape of a cylinder with a length dimension at least as long as a lengthdimension of a rod electrode and an outer diameter equal to that of theapertures in the plate electrode, and wherein inert material gaskets,PTFE gaskets or silicone gaskets are completely solid between the platesand is more than 80% open at a vicinity of the apterures in the plateelectrodes. Optionally, for each aperture, two diaphragms having a donutshape are placed at the top and bottom of apertures to completelyprevent mixing and/or contact of the oil or water or heat transferliquid or heat transfer solid with the electrolyte.

In an embodiment, a three-dimensional electrode array further comprisesone or more metal, glass, ceramic, steel, or polymer rods arranged suchthat each metal, glass, ceramic, steel or polymer rod extends a lengthalong an alignment axis passing through an aperture of each plateelectrode. Such metal, glass, ceramic, steel or polymer rods are useful,for example for providing structural integrity to the three-dimensionalelectrode array. Optionally, apertures which the metal, glass, ceramic,steel or polymer rods pass through are larger than apertures which theplurality of rod electrodes pass through.

In an embodiment, a three-dimensional electrode array further comprisesone or more metal, glass, ceramic, steel or polymer plates including anarray of apertures, wherein the one or more metal, glass, ceramic, steelor polymer plates are arranged in a substantially parallel orientationsuch that the each aperture of an individual metal, glass, ceramic,steel or polymer plate is aligned along the alignment axis passingthrough the apertures of each of the plate electrodes, Such metal,glass, ceramic, steel or polymer plates are useful, for example, forproviding structural integrity to the three-dimensional electrode array.

In an embodiment, a three-dimensional electrode array further comprisesa pump to flow a fluid positioned in a space between the plateelectrodes and the rod electrodes or a space between each of the plateelectrodes or a space inside each of the rod electrodes. Optionally, oneor more of the rod electrodes comprise hollow tubes.

Optionally, for use of different electrolytes, such as one between eachrod and the corresponding wall of the holes of the plates and anotherbetween the perforated plates, a thin membrane is included, for example,tens of micrometers thick, between the two electrolyte systems toseparate them. Such a membrane is useful when the two electrolytesystems are both fluid such as liquid, as an example similar to a thinO-ring. Optionally, the membrane is used to remove unwanted productsfrom the cell or to add assisting materials to the cell. Examples ofremoving unwanted products from the cell are some gas phases that happenas the product of the chemistry cell reactions, such as hydrogen gas,as, for example, is generated in Flow batteries or in Lead Acidbatteries, especially in flooded lead-acid batteries. In embodiments,the membranes used here are optionally inert materials such as PTFE orPE or other membrane products with desired pore sizes or chemistry orsurface behavior.

In an embodiment, a three-dimensional electrode further comprises one ormore dessicant plates including an array of apertures and comprising adessicant selected from the group consisting of silica gel, activatedcharcoal, calcium sulfate, calcium chloride, montmorillonite clay,molecular sieves and any combination of these, wherein the one or moredessicant plates are arranged in a substantially parallel orientationsuch that the each aperture of an individual dessicant plate is alignedalong the alignment axis passing through the apertures of each of theplate electrodes. Optionally, one or more dessicant plates comprise aninert coating or a PTFE coating. Inert coatings or PTFE coatings areuseful, for example, when the three-dimensional electrode array is a Libattery or a Li-air battery. Optionally, the inert coating or PTFEcoating increases the safety and/or performance the battery. In certainembodiments, a dessicant plate is removed from the three-dimensionalelectrode array after the dessicant plate is saturated with water.

In another aspect, also provided are methods for controlling atemperature of an electrochemical cell. A specific method of this aspectcomprises the steps of: providing an electrochemical cell comprising: aplurality of plate electrodes, wherein each plate electrode includes anarray of apertures, wherein the plate electrodes are arranged in asubstantially parallel orientation such that the each aperture of anindividual plate electrode is aligned along an alignment axis passingthrough an aperture of each of all other plate electrodes; and aplurality of rod electrodes, wherein the plurality of rod electrode arenot in physical contact with the plurality of plate electrodes andarranged such that each rod electrode extends a length along analignment axis passing through an aperture of each plate electrode;wherein a first surface area includes a cumulative surface area theplurality of plate electrodes, wherein a second surface area includes acumulative surface area of each aperture array and wherein a thirdsurface area includes a cumulative surface area of each of the pluralityof rod electrodes; wherein each of the plurality of plate electrodescomprises a current collector, wherein each of the plurality of rodelectrodes comprises a current collector or wherein each of theplurality of plate electrodes comprises a current collector and each ofthe plurality of rod electrodes comprises a current collector; andpositioning one or more of the current collectors in thermalcommunication with a heat sink or a heat source. Optionally, eachcurrent collector independently comprises a material selected from thegroup consisting of: a metal, a metal alloy, Cu, Ag, Au, Pt, Pd, Ti, Aland any combination of these.

In one embodiment, the positioning step comprises removing heat from atleast a portion of the electrochemical cell. In one embodiment, thepositioning step comprises adding heat to at least a portion of theelectrochemical cell. In one embodiment, the method further comprises astep of positioning one or more of the current collectors in thermalcommunication with a second heat sink or a second heat source.

Optionally, the electrochemical cell further comprises one or more heattransfer rods arranged such that each heat transfer rod extends a lengthalong an alignment axis passing through an aperture of each plateelectrode and the method further comprises the step of positioning oneor more of the heat transfer rods in thermal communication with the heatsink or the heat source.

In embodiments, a three-dimensional electrode comprises a flow battery.Optionally a three-dimensional electrode array, further comprises aplurality of tubes arranged such that each tube extends a length alongan alignment axis passing through an aperture of each plate electrodeand wherein at least one rod electrode is positioned within each tube.Optionally, a space within each tube between an inner wall of the tubeand a surface of a rod electrode is filled with a fluid, an electrolyte,an aqueous solution or a gas. Optionally, a space between an outer wallof each and wall of one or more apertures is filled with a fluid, anelectrolyte, an aqueous solution or a gas, for example different than afluid, an electrolyte, an aqueous solution or a gas that is presentwithin a space inside each tube. In embodiments, each fluid,electrolyte, aqueous solution or gas is flowing along an alignment axispassing through an aperture of each plate electrode. Optionally, a fluidinside each tube is flowing in a direction opposite to a fluid outsideeach tube.

In embodiments using different electrolytes, for example one betweeneach rod and the corresponding wall of the holes of the plates andanother between the perforated plates, a thin membrane is optionallyprovided, for example about tens of micrometers thick, between thedifferent electrolyte systems to separate them, for example when thedifferent electrolytes are both fluid such as liquid. Optionally, thethin membrane is a thin O-ring. Optionally, membranes can be used, abouttens of micrometers thin, in the shape of tubes, outer radius the sameas the holes, inner radius the same as the rods, which are placed aroundthe rods at the top and at the bottom of the plates.

Optionally, a membrane is used during operation of an electrochemicalcell to remove unwanted products from the cell or to add assistingmaterials to the cell. Example of removing unwanted products from thecell are gas phases that form as the product of the chemistry cellreactions, such as hydrogen gas as forms in flow batteries or in leadacid batteries, such as in flooded lead-acid batteries. The membranesused here are optionally inert materials such as PTFE or PE or othermembrane products with desired pore sizes or chemistry or surfacebehavior.

In one embodiment, the separator itself can be a flowing fluid. In anembodiment, that small particles with desired area to volume ratio aretransported in a flowing fluid separator and larger particles are nottransported in the flowing fluid separator.

In a specific embodiment, a three-dimensional electrode array furthercomprises a plurality of second tubes arranged such that each secondtube extends a length along an alignment axis passing through anaperture of each plate electrode and wherein at least one second tube ispositioned with each tube and wherein at least one rod electrode ispositioned within each second tube. In this embodiment, each second tubeprovides a further space in which an optional additional fluid can beflowed.

Another method of this aspect for controlling a temperature of anelectrochemical cell comprises the steps of: providing anelectrochemical cell comprising: a plurality of plate electrodes,wherein each plate electrode includes an array of apertures, wherein theplate electrodes are arranged in a substantially parallel orientationsuch that the each aperture of an individual plate electrode is alignedalong an alignment axis passing through an aperture of each of all otherplate electrodes; a plurality of rod electrodes, wherein the pluralityof rod electrode are not in physical contact with the plurality of plateelectrodes and arranged such that each rod electrode extends a lengthalong an alignment axis passing through an aperture of each plateelectrode; and one or more heat transfer rods arranged such that eachheat transfer rod extends a length along an alignment axis passingthrough an aperture of each plate electrode; wherein a first surfacearea includes a cumulative surface area the plurality of plateelectrodes, wherein a second surface area includes a cumulative surfacearea of each aperture array and wherein a third surface area includes acumulative surface area of each of the plurality of rod electrodes;wherein each of the plurality of plate electrodes comprises a currentcollector, wherein each of the plurality of rod electrodes comprises acurrent collector or wherein each of the plurality of plate electrodescomprises a current collector and each of the plurality of rodelectrodes comprises a current collector; and positioning one or more ofthe heat transfer rods in thermal communication with a heat sink or aheat source.

In yet another aspect, provided are methods of making electrode arrays.A specific method of this aspect comprises the steps of: providing aplurality of plate electrodes, wherein each plate electrode includes anarray of apertures; arranging the plurality of plate electrodes in asubstantially parallel orientation such that the each aperture of anindividual plate electrode is aligned along an alignment axis passingthrough an aperture of each of all other plate electrodes; providing aplurality of rod electrodes; and arranging the plurality of rodelectrodes such that the plurality of rod electrode are not in physicalcontact with the plurality of plate electrodes and such that each rodelectrode extends a length along an alignment axis passing through anaperture of each plate electrode.

In a specific method of this aspect, the step of providing a pluralityof plate electrodes comprises providing a plurality of currentcollectors and coating an electrode material on at least a portion ofthe surface of each current collector. In a specific method of thisaspect, the step of providing the plurality of rod electrodes comprisesproviding a plurality of current collectors and coating an electrodematerial on at least a portion of the surface of each current collector.

A specific method of this aspect comprises making an electrochemicalcell. For example a method for making an electrochemical cell furthercomprises a step of providing an electrolyte between each of theplurality of plate electrodes and each of the plurality of rodelectrodes, thereby making an electrochemical cell. Optionally, themethod further comprises a step of providing the electrolyte betweeneach of the plurality of plate electrodes and between each of theplurality of rod electrodes.

In another aspect, provided is a redox flow energy storage device. Adevice of this aspect comprises a positive electrode current collectorin the form of one or more rods, a negative electrode current collectorin the form of a grid or a grating of crossed bars, and an ion-permeablemembrane separating said positive and negative current collectors; apositive electrode disposed between the positive electrode currentcollector and the ion-permeable membrane; the positive electrode currentcollector and the ion-permeable membrane defining a positiveelectroactive zone accommodating the positive electrode; a negativeelectrode disposed between the negative electrode current collector andthe ion-permeable membrane; the negative electrode current collector andthe ion-permeable membrane defining a negative electroactive zoneaccommodating the negative electrode; wherein at least one of thepositive and negative electrode comprises a flowable semi-solid orcondensed liquid ion-storing redox composition capable of taking up orreleasing ions during operation of the cell.

In an embodiment of this aspect, both of the positive and negativeelectrodes comprise the flowable semi-solid or condensed liquidion-storing redox compositions. In an embodiment, one of the positiveand negative electrodes comprises the flowable semi-solid or condensedliquid ion-storing redox composition and the remaining electrode is aconventional stationary electrode. In an embodiment, the flowablesemi-solid or condensed liquid ion-storing redox composition comprises agel. In an embodiment, a steady state shear viscosity of the flowablesemi-solid or condensed liquid ion-storing redox composition is betweenabout 1 cP and 1,000,000 cP at the temperature of operation of the redoxflow energy storage device.

In an embodiment, the flowable semi-solid ion-storing redox compositioncomprises a solid comprising amorphous carbon, disordered carbon,graphitic carbon, graphene, carbon nanotubes or a metal-coated ormetal-decorated carbon. In an embodiment, the flowable semi-solidion-storing redox composition comprises a solid comprising a metal ormetal alloy or metalloid or metalloid alloy or silicon or anycombination of these. In an embodiment, the flowable semi-solidion-storing redox composition comprises a solid comprisingnanostructures selected from the group consisting of nanowires,nanorods, nanotetrapods and any combination of these. In an embodiment,the flowable semi-solid ion-storing redox composition comprises a solidcomprising an organic redox compound.

In an embodiment, a redox flow energy storage device further comprises astorage tank for storing the flowable semi-solid or condensed liquidion-storing redox composition, the storage tank in flow communicationwith the redox flow energy storage device. Optionally, a redox flowenergy storage device comprises an inlet for introduction of theflowable semi-solid or condensed liquid ion-storing redox compositioninto the positive/negative electroactive zone and an outlet for the exitof the flowable semi-solid or condensed liquid ion-storing redoxcomposition out of the positive/negative electroactive zone. Optionallya redox flow energy storage device further comprises a fluid transportdevice to enable flow communication, for example a fluid transportdevice comprising a pump. Optionally, a condensed-liquid ion-storingmaterial comprises a liquid metal alloy.

In another aspect, provided are methods of operating a redox flow energystorage device. A method of this aspect comprises the steps of providinga redox flow energy storage device, such as described above; andtransporting the flowable semi-solid or condensed liquid ion-storingredox composition into the electroactive zone during operation of thedevice. Optionally, at least a portion of the flowable semi-solid orcondensed liquid ion-storing redox composition in the electroactive zoneis replenished by introducing new semi-solid or condensed liquidion-storing redox composition into the electroactive zone duringoperation.

Optionally, a method of this aspect further comprises a step oftransporting depleted semi-solid or condensed liquid ion-storingmaterial to a discharged composition storage receptacle for recycling orrecharging. Optionally a method of this aspect further comprises a stepof applying an opposing voltage difference to the flowable redox energystorage device; and transporting charged semi-solid or condensed liquidion-storing redox composition out of the electroactive zone to a chargedcomposition storage receptacle during charging. Optionally, a method ofthis aspect further comprises the step of applying an opposing voltagedifference to the flowable redox energy storage device; and transportingdischarged semi-solid or condensed liquid ion-storing redox compositioninto the electroactive zone to be charged.

In another aspect, provided is a redox flow battery comprising a stackof perforated cells and a group of rods (for example of arbitrary aspectratio; from one that is a circle cross section to a very large numberthat is a rectangular cross section; the cross-section itself can varyfor example in size), and anolyte and catholyte compartments dividedfrom each other by an ionically selective and conductive separator andhaving respective electrodes; and anolyte and catholyte tanks, withrespective pumps and pipeworks to provide fluid communication betweenthe respective anolyte and catholyte tanks and compartements. In use,the pumps circulate the electrolytes to and from the tanks, to thecompartments and back to the tanks. Electricity optionally flows to aload. The electrolyte lines are optionally provided with tappings viawhich fresh electrolyte can be added and further tappings via whichspent electrolyte can be withdrawn, the respective tappings being foranolyte and catholyte. Optionally, on recharging, typically via acoupling for lines to all the tappings, a remote pump pumps freshanolyte and fresh catholyte from remote storages and draws spentelectrolyte to other remote storages.

Optionally, a redox flow battery further comprises an anode in acatholyte compartment, a cathode in an anolyte compartment and, an ionselective membrane separator between the compartments, a pair ofelectrolyte reservoirs, one for anolyte and the other for catholyte, andelectrolyte supply means for circulating anolyte from its reservoir, tothe anolyte compartment in the cell and back to its reservoir and likecirculating means for catholyte; the battery comprising: connections toits electrolyte reservoirs and/or its electrolyte supply means so thatthe battery can be recharged by withdrawing spent electrolyte andreplacing it with fresh electrolyte. Optionally, an electrolyte divideror membrane is a diaphragm between each rod and the walls of thecorresponding holes, or a thin tube shape that the inner and outer radiiare chosen to fit between the rod and the corresponding wall and is aslong as each of the rods or a thin tube shape as long as the thicknessof each of the perforated plates.

Without wishing to be bound by any particular theory, there can bediscussion herein of beliefs or understandings of underlying principlesrelating to the invention. It is recognized that regardless of theultimate correctness of any mechanistic explanation or hypothesis, anembodiment of the invention can nonetheless be operative and useful.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 A and 1B provide views of components of a three-dimensionalelectrode array embodiment.

FIGS. 2A and 2B provide front views of components of a three-dimensionalelectrode array embodiment showing alternate cross-sectional shapes.

FIGS. 3A and 3B provide views of a three-dimensional electrode arrayembodiment.

FIGS. 4A and 4B provide views of a three-dimensional electrode arrayembodiment comprising two different electrolytes.

FIGS. 5A and 5B provide views of a three-dimensional electrode arrayembodiment comprising elements for controlling the temperature of theelectrode array.

FIG. 6 provide views of a three-dimensional electrode array embodimentwith plate electrodes having a thickness larger than the spacing betweenplates.

FIGS. 7A and 7B provide views of a three-dimensional electrode arrayembodiment comprising a fluid and a solid in the interelectrode space.

FIG. 8 provide views of a three-dimensional electrode array embodimentcomprising closely spaced apertures in plate electrodes.

FIG. 9 provide views of a three-dimensional electrode array embodimentcomprising different rod electrode materials.

FIG. 10 provide views of a three-dimensional electrode array embodimentcomprising different plate electrode materials.

FIG. 11 provides a view of a three-dimensional electrode array in whicha fluid surrounding the electrodes is induced to flow.

FIG. 12 provides views of a three-dimensional electrode array comprisinghollow tube rod electrodes.

FIGS. 13A and 13B provide views of a three-dimensional electrode arraycomprising a first flowing fluid surround the plate electrodes and asecond flowing fluid surrounding the rod electrodes.

FIG. 14 provides views of a rod electrode embodiment.

FIGS. 15A and 15B provide views of a three-dimensional electrode arraycomprising hollow tube rod electrodes.

FIGS. 16A and 16B provide schematic drawings of a composite rodelectrode structure.

FIGS. 17A-17E provide schematic drawings of a three dimensionalelectrode array and optionally one or more flowing electrolytecomponents.

FIGS. 18A and 18B provide views of a composite rod electrode structurecomprising a porous rod.

FIG. 19 provides experimental data of charge and discharge cycles of anelectrochemical cell comprising a three-dimensional electrode array.

FIG. 20 provides a view of a single aperture of a plate electrodeshowing multiple rod electrodes.

FIG. 21 provides a schematic cross-sectional side view of athree-dimensional electrode array comprising branched rod electrodes.The inset shows a top view.

FIG. 22 provides a schematic cross-sectional side view of athree-dimensional electrode array comprising a bridge type structurelinking the rod electrodes. The inset shows a top view.

DETAILED DESCRIPTION

In general the terms and phrases used herein have their art-recognizedmeaning, which can be found by reference to standard texts, journalreferences and contexts known to those skilled in the art. The followingdefinitions are provided to clarify their specific use in the context ofthe invention.

Referring to the drawings, like numerals indicate like elements and thesame number appearing in more than one drawing refers to the sameelement. In addition, hereinafter, the following definitions apply:

The term “electrochemical cell” refers to devices and/or devicecomponents that convert chemical energy into electrical energy orelectrical energy into chemical energy. Electrochemical cells have twoor more electrodes (e.g., positive and negative electrodes) and anelectrolyte, wherein electrode reactions occurring at the electrodesurfaces result in charge transfer processes. Electrochemical cellsinclude, but are not limited to, primary batteries, secondary batteriesand electrolysis systems. In certain embodiments, the termelectrochemical cell includes fuel cells, supercapacitors, capacitors,flow batteries, metal-air batteries and semi-solid batteries. Generalcell and/or battery construction is known in the art, see e.g., U.S.Pat. Nos. 6,489,055, 4,052,539, 6,306,540, Seel and Dahn J. Electrochem.Soc. 147(3) 892-898 (2000).

The term “capacity” is a characteristic of an electrochemical cell thatrefers to the total amount of electrical charge an electrochemical cell,such as a battery, is able to hold. Capacity is typically expressed inunits of ampere-hours. The term “specific capacity” refers to thecapacity output of an electrochemical cell, such as a battery, per unitweight. Specific capacity is typically expressed in units ofampere-hours kg⁻¹.

The term “discharge rate” refers to the current at which anelectrochemical cell is discharged. Discharge current can be expressedin units of ampere-hours. Alternatively, discharge current can benormalized to the rated capacity of the electrochemical cell, andexpressed as C/(X t), wherein C is the capacity of the electrochemicalcell, X is a variable and t is a specified unit of time, as used herein,equal to 1 hour.

“Current density” refers to the current flowing per unit electrode area.

Electrode refers to an electrical conductor where ions and electrons areexchanged with electrolyte and an outer circuit. “Positive electrode”and “cathode” are used synonymously in the present description and referto the electrode having the higher electrode potential in anelectrochemical cell (i.e. higher than the negative electrode).“Negative electrode” and “anode” are used synonymously in the presentdescription and refer to the electrode having the lower electrodepotential in an electrochemical cell (i.e. lower than the positiveelectrode). Cathodic reduction refers to a gain of electron(s) of achemical species, and anodic oxidation refers to the loss of electron(s)of a chemical species. Positive electrodes and negative electrodes ofthe present electrochemical cell may further comprises a conductivediluent, such as acetylene black, carbon black, powdered graphite, coke,carbon fiber, graphene, and metallic powder, and/or may furthercomprises a binder, such polymer binder. Useful binders for positiveelectrodes in some embodiments comprise a fluoropolymer such aspolyvinylidene fluoride (PVDF). Positive and negative electrodes of thepresent invention may be provided in a range of useful configurationsand form factors as known in the art of electrochemistry and batteryscience, including thin electrode designs, such as thin film electrodeconfigurations. Electrodes are manufactured as disclosed herein and asknown in the art, including as disclosed in, for example, U.S. Pat. Nos.4,052,539, 6,306,540, 6,852,446. For some embodiments, the electrode istypically fabricated by depositing a slurry of the electrode material,an electrically conductive inert material, the binder, and a liquidcarrier on the electrode current collector, and then evaporating thecarrier to leave a coherent mass in electrical contact with the currentcollector.

“Electrode potential” refers to a voltage, usually measured against areference electrode, due to the presence within or in contact with theelectrode of chemical species at different oxidation (valence) states.

“Electrolyte” refers to an ionic conductor which can be in the solidstate, the liquid state (most common) or more rarely a gas (e.g.,plasma).

“Standard electrode potential” (E°) refers to the electrode potentialwhen concentrations of solutes are 1 M, the gas pressures are 1 atm andthe temperature is 25 degrees Celsius. As used herein standard electrodepotentials are measured relative to a standard hydrogen electrode.

“Active material” refers to the material in an electrode that takes partin electrochemical reactions which store and/or delivery energy in anelectrochemical cell.

“Cation” refers to a positively charged ion, and “anion” refers to anegatively charged ion.

“Electrical contact” and “electrical communication” refers to thearrangement of one or more objects such that an electric currentefficiently flows from one object to another. For example, in someembodiments, two objects having an electrical resistance between themless than 100 Ω are considered in electrical communication with oneanother. An electrical contact can also refer to a component of a deviceor object used for establishing electrical communication with externaldevices or circuits, for example an electrical interconnection.“Electrical communication” also refers to the ability of two or morematerials and/or structures that are capable of transferring chargebetween them, such as in the form of the transfer of electrons. In someembodiments, components in electrical communication are in directelectrical communication wherein an electronic signal or charge carrieris directly transferred from one component to another. In someembodiments, components in electrical communication are in indirectelectrical communication wherein an electronic signal or charge carrieris indirectly transferred from one component to another via one or moreintermediate structures, such as circuit elements, separating thecomponents.

“Thermal contact” and “thermal communication” are used synonymously andrefer to an orientation or position of elements or materials, such as acurrent collector or heat transfer rod and a heat sink or a heat source,such that there is more efficient transfer of heat between the twoelements than if they were thermally isolated or thermally insulated.Elements or materials may be considered in thermal communication orcontact if heat is transported between them more quickly than if theywere thermally isolated or thermally insulated. Two elements in thermalcommunication or contact may reach thermal equilibrium or thermal steadystate and in some embodiments may be considered to be constantly atthermal equilibrium or thermal steady state with one another. In someembodiments, elements in thermal communication with one another areseparated from each other by a thermally conductive material orintermediate thermally conductive material or device component. In someembodiments, elements in thermal communication with one another areseparated by a distance of 1 μm or less. In some embodiments, elementsin thermal communication with one another are provided in physicalcontact.

FIG. 1A provides views of a plate electrode 101 of a three-dimensionalelectrode array embodiment, including side 101A, top 101B, front 101Cand perspective 101D views. Here, plate electrode 101 includes aplurality of apertures 102, each having a circular shape. FIG. 1Bprovides views of a rod electrode 103 of a three-dimensional electrodearray embodiment, including front 103A, side 103B and perspective 103Dviews. Here, rod electrode 103 has a circular cross-sectional shape.

FIG. 2A provides a front view of a plate electrode. Here, plateelectrode includes a plurality of apertures of a variety of shapes. FIG.2B provides a front view of a plurality of rod electrodes showing avariety of useful cross-sectional shapes.

FIGS. 3A and 3B provide views of a three-dimensional electrode array304. FIG. 3A shows side 304A and top 304B views and FIG. 3B shows front304C and perspective 304D views. Three dimensional electrode array 304includes 6 plate electrodes 301 and 18 rod electrodes 303. Here, eachrod electrode 303 passes through an aperture 302 of each of the 6 plateelectrodes 301. Optionally, the vacant space between each of the plateelectrodes, between each of the rod electrodes and between each of theplate electrodes and each of the rod electrodes (i.e., in the apertures)is filled with an electrolyte

FIGS. 4A and 4B provide views of a three-dimensional electrode array404. FIG. 4A shows side 404A and top 404B views and FIG. 4B shows front404C and perspective 404D views. Three dimensional electrode array 404includes 6 plate electrodes 401 and 18 rod electrodes 403. Here, eachrod electrode 403 passes through an aperture 402 of each of the 6 plateelectrodes 401. Each plate electrode is flanked on both sides by a firstelectrolyte 405. Each rode electrode is surrounded by a secondelectrolyte 406. In this embodiment, second electrolyte 406 and rodelectrode 403 completely fill aperture 402. In this embodiment, firstelectrolyte 405 and second electrolyte 406 are different. For clarity,views 404A and 404B show a cross sectional view of rod electrode 403 andsurrounding second electrolyte 406.

FIGS. 5A and 5B provide views of a three-dimensional electrode array504. FIG. 5A shows side 504A and top 504B views and FIG. 5B shows front504C and perspective 504D views. Three dimensional electrode array 504includes 6 plate electrodes 501 and 18 rod electrodes 503. Here, eachrod electrode 503 passes through an aperture 502 of each of the 6 plateelectrodes 501. In this embodiment, each rod electrode includes acurrent collector 507. Optionally, one or more current collectors 507are placed in thermal communication with a heat sink or heat source tocontrol a temperature of the three-dimensional electrode array.

FIG. 6 provides views of a three-dimensional electrode array 604,showing side 604A and perspective 604B views. In this embodiment, thespace between plate electrodes 601 is smaller than the thickness of theplate electrodes 601.

FIG. 7A provides a side view of a three-dimensional electrode array704A, where the space between the plate electrodes 701 and the rodelectrodes 703 is filled with a fluid 708, such as a gas or a liquidelectrolyte. FIG. 7B provides a side view of a three-dimensionalelectrode array 704B, where the space between the plate electrodes 701is filled with a solid 709.

FIG. 8 provides views of a three-dimensional electrode array 804. FIG. 8shows front 804A, side 804B and perspective 804C views. In thisembodiment, there are 7 plate electrodes 801 and 48 rod electrodes 803.The apertures 802 in the plate electrodes are closely space in thisembodiment, for example at a distance less than 10% of the diameter ofthe apertures 802.

FIG. 9 provides views of a three-dimensional electrode array 904 andshows front 904A and perspective 904B views. In this embodiment, the rodelectrodes include two different materials, first rod electrode material902A and second rod electrode material 902B.

FIG. 10 provides views of a three-dimensional electrode array 1004 andshows side 1004A and perspective 1004B views. In this embodiment, theplate electrodes include two different materials, first plate electrodematerial 1001A and second plate electrode material 1001B. Optionalembodiments also include those with multiple plate electrode materialsand multiple rod electrode materials.

FIG. 11 provides views of a three-dimensional electrode array 1104,including a side view 1104A and a front view 1104B. In this embodiment,a thin tube 1110 fills each aperture in plate electrodes 1101. The spacebetween plate electrodes 1101 is filled with a first fluid 1108A. Forclarity, electrolyte 1108A is not shown in front view 1104B. Each thintube 1110 is filled with a second fluid 1108B surrounding rod electrode1103. Here, rod electrodes 1103 comprise an electron collector 1107. Inthis embodiment, a flow is provided such that fluid 1108B flows in thedirection shown by the arrows.

FIG. 12 provides views of a three-dimensional electrode array 1204 andshows perspective 1204A and side 1204B views. In this embodiment, rodelectrodes 1203 are constructed as hollow tubes, such that fluid canflow along the interior of the rod electrodes 1203 as indicated by thearrows. Certain embodiments comprising hollow rod electrodes are usefulfor a number of applications, including electrode array temperaturecontrol, fuel cell, metal-air batteries and flow batteries. In certainembodiments, rod electrodes 1203 comprise a porous material.

FIGS. 13A and 13B provides views of a three-dimensional electrode array1304, including perspective 1304A, front cross-sectional 1304B and top1304C views. This embodiment comprises 3 plate electrodes 1301 and 6 rodelectrodes 1303. Here, the space between the plate electrodes 1301 isfilled with a first fluid 1308A. For clarity, perspective view 1304Adoes not show first fluid 1308A. Surrounding each rod electrode 1303 isa thin tube 1310 filled with a second fluid 1308B. Each thin tube 1310fills an entire aperture in plate electrodes 1301. In frontcross-sectional view 1304B and top view 1304C, thin tubes 1310 areindicated by a dashed line. In embodiments, first fluid 1308A is inducedto flow within thin tubes 1310, for example, as shown by the arrows infront cross-sectional view 1304B. In embodiments, second fluid 1308B isinduced to flow across the space between plate electrodes 1301, forexample, as shown by the arrows in FIG. 13B. First fluid 1308A flows inthe spaces between plate electrodes 1301 and second fluid 1308B flowswithin thin tubes 1310.

Optionally, the plate electrodes 1301 comprise graphite and areoptionally useful as an anode. Optionally, the rod electrodes 1303useful as a cathode. Optionally, the rod electrodes 1303 comprise acarbon shell and include electron collectors (not shown) comprisingcopper. Optionally, first fluid 1308A and second fluid 1308independently comprises electrolytes. In an embodiment wherethree-dimensional electrode array 1304 is a component of a semi-solidbattery, first fluid 1308A comprises a first electrolyte and a firstactive material and second fluid 1308B comprises a second electrolyteand a second active material. In an embodiment where three-dimensionalelectrode array 1304 is a component of a flow battery, first fluid 1308Acomprises a first electrolyte second fluid 1308B comprises a secondelectrolyte. In an embodiment where three-dimensional electrode array1304 is a component of a fuel cell, first fluid 1308A comprises a fuel,such as H₂, and second fluid 1308B comprises an oxygen containing fluid,such as air.

FIG. 14 provides views of a rod electrode embodiment 1403, including endview 1404A and cross-sectional view 1404B. In this embodiment, each rodelectrode 1403 comprises an electrode pair, including rod inner core1403A and rod outer shell 1403B. In this embodiment, rod inner core1403A comprises a first electron collector 1407A. In this embodiment,rod outer shell 1403B comprises a second electron collector 1407B.Between rod inner core 1403A and rod outer core 1403B is material 1408.In certain embodiments, each rod electrode 1403 is an electrochemicalcell, and material 1408 comprises an electrolyte.

Rod electrodes of the embodiment shown in FIG. 14 are useful, forexample, in any three-dimensional electrode array described herein.Optionally, the rod electrode inner core and a plate electrode compriseidentical or substantially identical materials. Embodiments of thisaspect are useful, for example, for increasing the ratio of the amountof the rod inner core/plate material to the amount of rod outer corematerial.

FIGS. 15A and 15B provide three-dimensional views of a three-dimensionalelectrode array 1504. In this embodiment, many plate electrodes arestacked, sandwiching materials, such as a solid electrolyte, between theplate electrodes. Many rod electrodes are shown, including a currentcollector. Optionally, the current collectors are held under tension toprovide structural rigidity to the electrode array.

FIGS. 16A and 16B provide views of a composite rod electrode structure.FIG. 16A provides an end view of the composite rod electrode structure1600 having electrodes 1601, electrode 1602, current collector 1603 andelectrolyte 1604. FIG. 16B provides a cross sectional side view of thecomposite rod electrode 1600 also showing electrodes 1601, electrode1602, current collector 1603 and electrolyte 1604. In an embodiment,electrodes 1601 are an anode and electrode 1602 is a cathode.Alternatively, the invention includes composite rod electrodes whereinelectrodes 1601 is a cathode and electrode 1602 is an anode. In anembodiment, composite rod electrode structure 1600 provides anelectrochemical cell, a fuel cell, a flow cell, a metal air battery, ora supercapacitor device.

FIGS. 17A-17E provide schematic drawings of three-dimensional electrodearrays, optionally including one or more flowing electrolyte components.FIG. 17A provides a side view of an electrode array electrode structure1700A having plate electrodes 1701A, rod electrodes 1702A, firstelectrolyte 1703A, second electrolyte 1704A and membrane 1705A. As shownin this figure, rod electrodes 1702A extend through holes provided inplate electrodes 1701A. Rod electrodes 1702A are provide in an arraygeometry and plate electrodes 1701A are provided in a stackedconfiguration. In an embodiment, plate electrodes 1701A and rodelectrodes 1702A are solid electrodes. In an embodiment, firstelectrolyte 1703A and second electrolyte 1704A are independently asolid, a gel or a fluid electrolyte. In an embodiment, for example,first electrolyte 1703A and second electrolyte 1704A are the sameelectrolyte. In an alternative embodiment, for example, firstelectrolyte 1703A and second electrolyte 1704A are differentelectrolytes. In an embodiment, membrane 1705A is a solid membraneproviding a barrier between plate electrodes 1701A and rod electrodes1702A.

FIG. 17B provides a side view of an electrode array structure 1700Bhaving plate electrodes 1701B, rod electrodes 1702B and membrane 1705Band demonstrating an embodiment including a flowing electrolyteconfiguration, for example, having a flowing first electrolyte 1703B anda flowing second electrolyte 1704B. In FIG. 17B, the arrows indicate thedirection of flow of electrolytes. In an embodiment, electrolyte 1703Bis a flowing fluid that optionally includes active nanoparticles and/ormicroparticles, for example, which participate in oxidation—reductionreactions. In an embodiment, electrolyte 1704B is a flowing fluid thatoptionally includes active nanoparticles and/or microparticles, forexample, nanoparticles and/or microparticles which participate inoxidation—reduction reactions.

FIG. 17C provides a side view of an electrode array structure 1700C, forexample for an electrochemical cell, having plate electrodes 1701C, rodelectrodes 1702C, first electrolyte 1703C, second electrolyte 1704C,membrane 1705C and space 1706C. In an embodiment, for example, space1706C is filled with liquid to control the temperature of the cell or toremove the unwanted products from the cell, for example, via membrane1705C. In an embodiment, for example, space 1706C is filled withelectrolyte or with porous PE or porous PP and electrolyte.

FIGS. 17D and 17E provide a side view of the composite rod electrodestructure 1700C used in a flowing electrolyte configuration, forexample, having a flowing first electrolyte 1703C and a flowing secondelectrolyte 1704C. In FIGS. 17D and 17E, the arrows indicate thedirection of flow of electrolyte. As shown in FIG. 17D, for example, thesystem may have a flowing first electrolyte 1703C and a flowing secondelectrolyte 1704C. As shown in FIG. 17D, for example, the system mayhave a flowing first electrolyte 1703C, a flowing second electrolyte1704C and a flowing electrolyte in space 1706C. To prevent mixing offirst electrolyte 1703C and second electrolyte 1704C, a barrier 1707C isoptionally provided, for example comprising a thin tube of inertmaterial.

FIGS. 18A and 18B provide views of a composite rod electrode comprisinga porous rod. FIG. 18A provides an end view of the composite rodelectrode structure 1800 having an anode or cathode 1801, currentcollector 1803, an electrolyte 1804, and pores 1805. FIG. 18B provides across sectional view of the composite rod electrode 1800 also having ananode or cathode 1801, current collector 1803, an electrolyte 1804, andpores 1805. In an embodiment, electrolyte 1804 comprises a fluid. In anembodiment, electrolyte 1804 comprises a solid. In an embodiment,electrolyte 1804 comprises a fluid and a separator. In an embodiment,pores 1805 provide for fluid communication of the electrolyte 1804inside the composite rod electrode structure 1800 to components outsideof the rod electrode structure 1800, for example plate electrodes andthe space between the plate electrodes.

FIG. 19 provides data showing a charge-discharge curve for cycling anelectrochemical cell embodiment comprising a three-dimensional electrodearray including Ewe versus time and Current (I) versus time. For thisembodiment, the cell comprises two parallel plates comprised of LiMn₂O₄,each of dimensions 10 mm×10 mm×0.2 mm with an Al current collector of0.01 mm thick in the middle of the LiMn₂O₄ plate electrode. The cellalso comprises four graphite rod electrodes of 2.5 mm diameter with a0.1 mm diameter copper electron collector core. The voltage, Ewe, shownin FIG. 18, is with respect to the standard hydrogen electrode (SHE).

FIG. 20 provides a view of a single aperture of a plate electrodeshowing multiple rod electrodes 2001 positioned within the single plateelectrode. Here, rod electrodes include an electron collector 2003 andthe aperture is filled with a fluid 2004. Optionally, fluid 2004 is anelectrolyte. In an embodiment, fluid 2004 is a flowing fluid thatoptionally includes active nanoparticles and/or microparticles, forexample, nanoparticles and/or microparticles which participate inoxidation—reduction reactions.

FIG. 21 provides a schematic cross-sectional side view of athree-dimensional electrode array comprising branched rod electrodes.The inset shows a top view. Here, the electrode array comprises plateelectrodes 2101, rod electrodes 2102 and electrolyte 2103. A space isprovided between plate electrodes 2101 and is optionally filled with asolid, fluid or gel electrolyte 2104. For clarity, the inset view doesnot show electrolyte 2104. Rod electrodes 2102 branch along lateraldimensions from an aperture in plate electrodes 2101. Optionally,electrolyte 2103, which separates rod electrodes 2102 from plateelectrodes 2101, is applied as a coating on the rod electrode 2102.

FIG. 22 provides a schematic cross-sectional side view of athree-dimensional electrode array comprising a bridge type structurelinking the rod electrodes. The inset shows a top view. Here, theelectrode array comprises plate electrodes 2201, rod electrodes 2202 andelectrolyte 2203. A space (not explicitly shown in the cross-sectionalview) is provided between plate electrodes 2201 and is optionally filledwith a solid, fluid or gel electrolyte 2204. Here, the inset view showselectrolyte 2204 surrounding rod electrode 2202 and electrolyte 2203.Rod electrodes 2202 form bridges to neighboring rod electrodes 2203along lateral dimensions from an aperture in plate electrodes 2101.Optionally, electrolyte 2203, which separates rod electrodes 2202 fromplate electrodes 2201, is applied as a coating on the rod electrode2202.

As will be understood by one of skill in the art, the figures providedare illustrative of embodiments of the invention. Unless otherwiseindicated, the dimensions shown in the figures are not intended to be toscale. Orientations of embodiments shown include both horizontal andvertical orientations; that is, where an embodiment is shown with asingle orientation, another orientation, rotated 90° is also disclosed.

Note that in all designs, some of the holes are optionally used only forstructural integrity, by using metal or ceramic or glass or polymerrods, for example, steel rods. These holes optionally have largerdiameter than the electrode rod holes. Some of the space bottom theparallel plates are optionally also used only for structural integrity,by using metal or ceramic plates. For example by using steel plates orglass plates.

An advantage of the designs described herein is that the maintenance canbe done easier and faster, for example, when the cell is composed ofmany individual rods and plates. Another advantage is that, as theratios of volume/foot-print surface area and active surface area/footprint surface area can be increase significantly over prior art designs,there is much less of the problem of electrolyte evaporation (which is amajor problem, for example, in metal air batteries and in fuel cells) orambient air-moisture contamination.

Optionally, current collectors are included in a three-dimensional cell.Not only are current collectors useful for transporting electrons incharge-discharge, but also current collectors optionally providemechanical-structural stability to the cell. Optionally, some currentcollectors are used to help with the temperature control of the cell andthus can hinder overheating of the battery and can increase theperformance and life.

Optionally, the current collector/temperature control element is solidor is liquid such as a molten metal or molten salt flowing inside atube-pipe or it can be a metallic tube, for example Al or Cu or Ni totransport electrons, where inside the tube there is a fluid such as airor a liquid coolant such as oil or water or heat transfer fluid that canflow from one end to the other end, and be useful for controlling thetemperature of the cell, for example for mid-large scale applicationssuch as electric cars, renewable energy storage and grid storage.

For embodiments comprising a fluid electrolyte, a separator isoptionally included between the rods and the walls of the plates toavoid their contact. For example, useful materials include PE or PP or acombination from Celgard co. The thickness is, for example, between0.010 mm to 0.5 mm, or about 0.02 mm.

Note that graphite alone or combined with metals such as Al, areoptionally useful as current collectors. Optionally, an electrolytecomprises an imide salt.

An important advantage of the current design is longer cycle life. Asthe cell is much more homogeneous comparing to the conventional design,the materials deformations and the temperature distribution are morehomogeneous, resulting in lower stresses, lower cracks, less fatigue,and thus higher cycle life of the cell.

The distance between the parallel plates is optionally filled with amaterial solely for temperature control such as heat pipe or heat pinthat can use thermal conductivity and phase transition. This isespecially useful in mid-large scales, such as in electric cars and gridstorage. As an example, such a material is a screen made of metals, suchas thin steel or copper (e.g., a few micrometers thick for small cellsto a few centimeters thick for bigger cells). There is no contactbetween the screen and the rods.

Optionally, the space between plates is optionally filled with oil orwater or a heat transfer fluid to maintain the temperature of the cellat a specified temperature by using a thermostat. This liquid isoptionally separated from the electrolyte between the rods and thehole-walls by using inert material (as an example PTFE or Silicone)gaskets with the shape of a long cylinder (as long as the rods) withouter diameter equals that of the holes, and thickness of, as an exampleabout 1 mm, which is completely solid between the plates and is morethan 80% open at the vicinity of the walls of the holes. Further, foreach hole, two diaphragms, donut shape: each 0.05 wide and 0.05 thick,are optionally placed at the top and bottom of the holes to completelyprevent the mixture of the cooling liquid with the electrolyte.

Optionally, a gas or liquid coolant is used for controlling an electrodearray temperature. Useful gas coolants include air, hydrogen, inertgases such as nitrogen, helium or carbon dioxide or Sulfur hexafluorideor steam. Useful liquid coolants include oil, mineral oil, castor oil,water, deionized water, heavy water, liquefied neon, molten salts,NaF—NaBF₄, FLiBe, FLiNaK, liquid lead, liquid lead-bismuth alloy,silicone oils, fluorocarbon oils, Freons, Halomethanes, ammonia, sulfurdioxide, carbon dioxide, Polyalkylene glycol, or can be a solution of anorganic chemical in water, such as betaine, ethylene glycol, diethyleneglycol, propylene glycol. Useful coolants further include liquids suchas liquid nitrogen, liquid helium, liquid hydrogen. The coolant isoptionally a solid such as dry ice or water ice. Useful coolants alsoinclude nanofluids or semisolids comsisting of a carrier liquid such aswater dispersed with tiny (10 nm to a few mm size) particles made ofCuO, Aluminia, titanium dioxide, carbon nanotubes, carbon powders,silica, or metals such as copper or silver.

Optionally, each of the electrodes or electrolytes or dielectricmaterials are a heterogeneous material such as a layered composite, suchas a first material with a second coating at least on one side of it.

The invention may be further understood by the following non-limitingexamples.

EXAMPLE 1 Industrial Applications

Worldwide, there are ever-growing demands for electricity. At the sametime, there is an increasing push to harness reusable sources of energyto help meet these increasing electricity demands and offset and/orreplace traditional carbon-based generators which continue to depletenatural resources around the world.

Many solutions have been developed to collect and take advantage ofreusable sources of energy, such as solar cells, solar mirror arrays,and wind turbines. Solar cells produce direct current energy fromsunlight using semiconductor technology. Solar mirror arrays focussunlight on a receiver pipe containing a heat transfer fluid whichabsorbs the sun's radiant heat energy. This heated transfer fluid isthen pumped to a turbine which heats water to produce steam, therebydriving the turbine and generating electricity. Wind turbines use one ormore airfoils to transfer wind energy into rotational energy which spinsa rotor coupled to an electric generator, thereby producing electricitywhen the wind is blowing. All three solutions produce electricity whentheir associated reusable power source (sun or wind) is available, andmany communities have benefited from these clean and reusable forms ofpower.

When the sun or wind is not available, such solutions are not producingany power then nonreusable energy solutions are often turned, some formof energy storage is needed to store excess energy from the reusablepower sources during power generation times to support energy demandswhen the reusable power source is unavailable or unable to meet peakdemands for energy. So far people have tried molten salt thermal storageas a candidate to store heat as a form of energy; however the technologyis very costly.

This example describes an electrochemical energy storage apparatus. Theelectrochemical energy storage apparatus has at least a positiveterminal and a negative terminal which are electrically insulated fromeach other. It also has a non-electro-conductive material, which can besolid or fluid or gas, between the two terminals. This medium is aconductor for some of the ions of materials used for the terminals.Electro conductive materials such as metals can be used on the outersurface of the terminals to facilitate the passage of the electrons.Related methods of constructing and controlling an electro chemicalenergy storage system are also disclosed. An electro chemical energypower system utilizing an electrochemical energy storage apparatus isfurther disclosed, as is a charge exchanger for the electrochemicalenergy storage system.

The medium between the terminals can be selected from the groupconsisting of a salt, a salt mixture, a eutectic salt mixture, lithiumnitrate, potassium nitrate, sodium nitrate, sodium nitrite, calciumnitrate, lithium carbonate, potassium carbonate, sodium carbonate,rubidium carbonate, magnesium carbonate, lithium hydroxide, lithiumfluoride, beryllium fluoride, potassium fluoride, sodium fluoride,calcium sulfate, barium sulfate, lithium sulfate, lithium chloride,potassium chloride, sodium chloride, iron chloride, tin chloride, andzinc chloride, sulphuric acid, water and any combination of these.

The terminals can have any shape and geometry, such as plates or tubesor cylinders or parts of them.

Optionally, the whole storage system is contained in a non-conductivecontainer.

Optionally, non-conductive spacers can be used between the terminalsespecially when the medium is a fluid or gas to prevent short circuitthrough physical contact.

Optionally, the container comprise a conductive material or anon-conductive material such as a material selected from the groupconsisting of plastics, ceramics, firebrick, refractory material,castable refractories, refractory brick, mixtures of alumina (Al₂O₃),silica (SiO₂), magnesia (MgO), zirconia (ZrO₂), chromium oxide (Cr₂O₃),iron oxide (Fe₂O₃), calcium oxide (CaO), silicon carbide (SiC), carbon(C); metallic materials, plain carbon steels; alloy steels, manganese,silicon, silicon-manganese, nickel, nickel chromium, molybdenum,nickel-molybdenum, chromium, chromium-molybdenum, chromiummolybdenum-cobalt, silicon-molybdenum, manganese-silicon-molybdenum,nickel-chromium molybdenum, silicon-chromium-molybdenum,manganese-chromium-molybdenum, manganese silicon-chromium-molybdenum,vanadium, chromium-vanadium, silicon-chromium-vanadium,manganese-silicon-chromium-vanadium, chromium-vanadium-molybdenum,manganese-silicon chromium-vanadium-molybdenum, chromium-tungsten,chromium-tungsten-molybdenum, chromium-tungsten-vanadium,chromium-vanadium-tungsten-molybdenum, chromiumvanadium-tungsten-cobalt, chromium-vanadium-tungsten-molybdenum-cobalt;stainless steels, austenitic, ferritic, martensitic, duplex,precipitation-hardening, superaustenitic, superferritic; nickel alloys,nickel-chromium-iron, nickel-chromium-iron-aluminum,nickel-chromium-iron aluminum-titanium,nickel-chromium-iron-aluminum-titanium-niobium, nickel-chromium-ironcobalt-molybdenum, nickel-chromium-iron-niobium,nickel-chromium-iron-molybdenum niobium,nickel-chromium-iron-molybdenum-niobium-titanium-aluminum,nickel-chromium molybdenum-iron-tungsten,nickel-chromium-iron-molybdenum-copper-titanium, nickelchromium-iron-molybdenum-titanium,nickel-iron-cobalt-aluminum-titanium-niobium, nickel copper,nickel-copper-aluminum-titanium, nickel-molybdenum-chromium-iron, nickelchromium-molybdenum-copper,nickel-chromium-molybdenum-iron-tungsten-copper, andnickel-chromium-molybdenum.

The base for the storage system comprises a material selected from thegroup consisting of earth, firebrick, refractory material, concrete,castable refractories, refractory concrete, refractory cement,insulating refractories, gunning mixes, ramming mixes, refractoryplastics, refractory brick, mixtures of alumina (Al₂ 03), silica (SiO₂),magnesia (MgO), zirconia (ZrO₂), chromium oxide (Cr₂O₃), iron oxide(Fe₂O₃), calcium oxide (CaO), silicon carbide (SiC), carbon (C);metallic materials, carbon steels; alloy steels, manganese, silicon,silicon-manganese, nickel, nickel-chromium, molybdenum,nickel-molybdenum, chromium, chromium-molybdenum,chromium-molybdenum-cobalt, silicon-molybdenum,manganese-silicon-molybdenum, nickel chromium-molybdenum,silicon-chromium-molybdenum, manganese-chromium-molybdenum,manganese-silicon-chromium-molybdenum, vanadium, chromium-vanadium,silicon-chromium vanadium, manganese-silicon-chromium-vanadium,chromium-vanadium-molybdenum,manganese-silicon-chromium-vanadium-molybdenum, chromium-tungsten,chromium-tungsten molybdenum, chromium-tungsten-vanadium,chromium-vanadium-tungsten-molybdenum,chromium-vanadium-tungsten-cobalt,chromium-vanadium-tungsten-molybdenum-cobalt; stainless steels,austenitic, ferritic, martensitic, duplex, precipitation-hardening,superaustenitic, superferritic; nickel alloys, nickel-chromium-iron,nickel-chromium-iron-aluminum, nickel chromium-iron-aluminum-titanium,nickel-chromium-iron-aluminum-titanium-niobium, nickelchromium-iron-cobalt-molybdenum, nickel-chromium-iron-niobium,nickel-chromium-iron molybdenum-niobium,nickel-chromium-iron-molybdenum-niobium-titanium-aluminum, nickelchromium-molybdenum-iron-tungsten,nickel-chromium-iron-molybdenum-copper-titanium,nickel-chromium-iron-molybdenum-titanium,nickel-iron-cobalt-aluminum-titanium-niobium, nickel-copper,nickel-copper-aluminum-titanium, nickel-molybdenum-chromium-iron, nickelchromium-molybdenum-copper,nickel-chromium-molybdenum-iron-tungsten-copper, andnickel-chromium-molybdenum.

In embodiments, an energy storage system can be positioned such that theterminals face vertical, such that the terminals face the ground, suchthat the terminals face horizontal, such that the terminals do not facethe ground, for example, perpendicular to the ground.

Optionally, a group of terminals can be used in parallel or seriesconfigurations.

Optionally, the terminals comprise material selected from the groupconsisting of iron oxides; metals; lithium phosphates; sodiumphosphates; plain carbon steels; graphite, lead metal, lead dioxide,alloy steels, manganese, silicon, silicon-manganese, nickel,nickel-chromium, molybdenum, nickel-molybdenum, chromium,chromium-molybdenum, chromium-molybdenum-cobalt, silicon-molybdenum,manganese-silicon-molybdenum, nickel-chromium-molybdenum,silicon-chromium-molybdenum, manganese-chromium-molybdenum,manganese-silicon-chromium molybdenum, vanadium, chromium-vanadium,silicon-chromium-vanadium, manganese-silicon chromium-vanadium,chromium-vanadium-molybdenum, manganese-silicon-chromiumvanadium-molybdenum, chromium-tungsten, chromium-tungsten-molybdenum,chromium tungsten-vanadium, chromium-vanadium-tungsten-molybdenum,chromium-vanadium-tungsten cobalt,chromium-vanadium-tungsten-molybdenum-cobalt; stainless steels,austenitic, ferritic, martensitic, duplex, precipitation-hardening,superaustenitic, superferritic; nickel alloys, nickel chromium-iron,nickel-chromium-iron-aluminum, nickel-chromium-iron-aluminum-titanium,nickel-chromium-iron-aluminum-titanium-niobium,nickel-chromium-iron-cobalt-molybdenum, nickel-chromium-iron-niobium,nickel-chromium-iron-molybdenum-niobium, nickel-chromiumiron-molybdenum-niobium-titanium-aluminum,nickel-chromium-molybdenum-iron-tungsten,nickel-chromium-iron-molybdenum-copper-titanium,nickel-chromium-iron-molybdenum titanium,nickel-iron-cobalt-aluminum-titanium-niobium, nickel-copper,nickel-copper aluminum-titanium, nickel-molybdenum-chromium-iron,nickel-chromium-molybdenum-copper,nickel-chromium-molybdenum-iron-tungsten-copper, andnickel-chromium-molybdenum.

As an example the system used for a 400 MWh storage can be made of aplates of 35 m by 35 m with the thickness of a few centimeters as theterminals and medium of a few centimeters thickness between them. Theplates can be parallel to each other and they can be either standingvertically in or above the ground or they can be parallel to the groundin or above the ground.

The materials used as an example can be an oxide such as lithium ionphosphate, and graphite as the plates with a medium of lithium salts,such as LiPF₆, LiBF₄, or LiClO₄, in an organic solvent, such as ether.Depending on the materials used, different operating temperatures arecontemplated including room temperature.

Another example can be the same geometry as above but with the materialsof lead metal (Pb) and lead (IV) dioxide (PbO₂) in a medium of about33.5% v/v (6 Molar) sulphuric acid (H₂SO₄).

The electricity source from the energy source is connected to the twoterminals. The electric energy makes one of the terminals to get reducedand the other one to get oxidized. This way the ions from one terminalleave the terminal and go the medium. The medium transfers the ions tothe opposite terminal. This way the chemical energy is stored in thesystem. Then the electricity source is opened from the storage system.

When it is desired to use the stored energy, the two plates areconnected to each other by a conductive material, with the userapplication between the two ends of the conductive material.

The chemistry used in the system can be any known chemistry of batteriessuch as Lead-Acid battery, NaS battery, Metal-Air battery, Li-ionbattery, etc., however the electrode geometry is different. Optionally,it is in larger scales and it can be honey-comb geometry or any otherporous geometry. Thin honey comb structures are optionally used, tominimum stresses due to shape changes in charge/discharge. Optionally, asponge type matrix filled with the electrode material can be utilized.The thickness of the plates or the diameter of the cables/rods/wires canoptionally be millimeters or centimeters. The width and length of theplates and the length of the cables/rods/wires can optionally becentimeters or meters. The plates and cables/rods/wires can be connectedin any combination of parallel or series.

The system can be buried under the ground or can be put in a room tostay away from the environmental hazards including temperature changes.All the solid parts can be controlled at the boundaries such as bypulling the cables/rods/wires to minimize the risk of electrical shortsin the system.

EXAMPLE 2 Electrochemical Cells

Many scientists have been working on the chemistry of batteries. Thisexample describes a new configuration for the electrodes that can beused for any chemistry, including anode, cathode and electrolyte, whichcan result in higher power/energy density batteries, faster batteries,lighter batteries, cheaper batteries, and more durable batteries.

In designing the most historically successful industrial batteries, thelead-acid battery configuration played a key role. Plante's and Faure'schanges of the configurations resulted in the commercialization oflead-acid battery which has been the dominant battery for more than acentury.

The new configuration described here can be used for primary andsecondary batteries. It can transform primary batteries to secondarybatteries and it can provide better cyclability and safety for secondarybatteries. As an example, the new configuration can be used for primaryand secondary lithium batteries. Lithium metal anode in Lithium basedbatteries has energy density an order of magnitude higher than currentlyused carbon anode. Though, due to the formation of dendrites on lithiumanode during the recharging process, the cell may short circuit andexplode. For this reason in rechargeable batteries, currently, carbonanode is the only option. In addition to lower energy density comparingto lithium metal, carbon anodes needs special electrolytes, which addsto the cost. The new configuration described herein solves the shortingproblem in Li-metal anodes. This will result in much cheaperrechargeable batteries that can last longer than available lithium basedbatteries.

Currently, the active electrochemical materials compose only one thirdof the weight of a battery pack. The problem is that the prior artbattery configurations limit the size of the battery. At the macro-scaleone goal of the present systems is to remove the constraints on the sizeof the battery pack by changing the configuration. This makes thebatteries more efficient, as there is less need of the supportingmaterials that do not play any electrochemical roles. It results ingetting closer to ideal battery systems for electric vehicles. Inaddition, it results in lighter and cheaper batteries that can be usedfor large-scale energy storage systems needed for grid electricitystorage and also renewable energy sources such as solar farms and windfarms.

The new configuration/geometry described herein can improve all batterychemistries including those with the Li-metal anode. In this novel3-dimensional configuration, perforated anode (or cathode) plates areplaced parallel to each other with electrolyte between them. Cathode (oranode) rods go through the plate holes to form a mesh. The radius ofeach rod is less than that of the holes to allow for the electrolytepassage between the rods and the holes. When using lithium metal plates,the wall of the holes can be covered with an inert material so thatdendrites do not happen between the opposite electrodes but happenbetween the lithium plates.

Each plate can have different geometries such as rectangular plates,cylindrical plates or any other geometry. The thickness of each of theplates can be from 20 nm to 5 cm, as an example around 100 micrometersfor lithium batteries and 2 mm for lead-acid batteries. The holes of theplates can have different geometries such as cylindrical or rectangularor any other geometry. The radius of the holes can be from 10 nm to 2cm, as an example 50 micrometers for lithium batteries and 500micrometers for lead-acid batteries. The rods can have differentgeometries similar to the holes with the radius smaller than the holes.The surface fraction of the holes is arbitrary. The distance between theholes can be a few nanometers to a few millimeters, as an example can bea few micrometers in lithium batteries and a few hundred micrometers inlead acid batteries. The plates can be from 20 nm to 20 meterslong/wide, as an example 10 mm for lithium batteries and 10 cm forlead-acid batteries. The distance between any two plates can be from 10nm to 5 cm, as an example 10 micrometers, as an example 1 micrometer forlithium batteries and 1 mm for lead acid batteries. The inert material,as shown in the picture, covers the walls of the holes. It can be madeof any material that doesn't have any chemical or electrical reactionwith the electrodes or electrolyte, such as rubber, plastic, orceramics. Its thickness can be from a few nanometers to a fewmillimeters.

EXAMPLE 3 Lithium Batteries

This example focuses on lithium batteries. A great degree of attentionhas been devoted to rechargeable Lithium batteries in the past fewyears, but still there are many unknowns that should be scrutinized.Here, a new configuration of the electrodes is described. As an examplea Li-metal anode is considered. Lithium metal used as an anode activematerial has a very high theoretical capacity of 3860 Ah/kg, which isthe highest among metallic anode materials. In addition, the standardelectrode potential of lithium is high (−3.045V vs SHE). This makeslithium metal a very attractive anode material.

Because of safety problems, a safer lithium cell, the lithium ion cell,was developed and is now commercially available. Currently Li-metalanodes are only used in primary lithium batteries. They can't be used inrechargeable cells due to the lithium dendrites that form on the lithiummetal anode in the recharging process. The dendrites make shorts betweenthe opposite electrodes and cause fire and explosion of the cell.

However, the high energy density of lithium metals cells is still veryattractive, if the safety problem can be overcome. The conductivity ofthe nonaqueous electrolyte used in the AA-size lithium metal anodeprototype cells is one order of magnitude lower than that of an aqueoussystem. Thus, if one can solve the safety problem, the rate of chargingof the battery will improve a lot.

The new configuration/geometry described herein improves all batterychemistries including those with the Li-metal anode. In this novel3-dimensional configuration, perforated anode plates are placed parallelto each other with electrolyte between them. The cathode rods go throughthe plate holes to form a mesh. The radius of each rod is less than thatof the holes to allow for the electrolyte passage between the rods andthe holes. When using lithium metal plates, the wall of the holes can becovered with an inert material so that dendrites do not happen betweenthe opposite electrodes but happen between the lithium plates. Eachplate can have different geometries such as rectangular plates,cylindrical plates or any other geometry. The thickness of each of theplates can be from 20 nm to 5 cm, as an example around 100 micrometers.The holes of the plates can have different geometries such ascylindrical or rectangular or any other geometry. The radius of theholes can be from 10 nm to 2 cm, as an example 50 micrometers. The rodscan have different geometries similar to the holes with the radiussmaller than the holes. The plates can be from 20 nm to 20 meterslong/wide. The distance between any two plates can be from 10 nm to 5cm, as an example 10 micrometers.

There are many possible choices for the cathode. The most popular arelithium manganese dioxide, lithium cobalt, and FeS₂. The suggestedconfiguration/geometry works for any chemistry of batteries includingthe lithium-air chemistry.

The temperature of the cell also plays an important role on the safetyand cyclability of the battery. A novel approach is suggested here. Ifcurrent collectors are needed the cathode current collector is in thecore of the rods; the anode current collector, if needed, can be formedof a grid in the plate. As each current collector runs in the entirecell, by using the current collectors as heat conductive material we canset the cell temperature very cheap and effectively.

EXAMPLE 4 Lead-Acid Batteries

The lead acid cell can be demonstrated using sheet lead plates for thetwo electrodes. However such a construction produces only around oneampere for roughly postcard sized plates, and for only a few minutes.The plate dimensions are typically about 50×50×1.5 mm. Since thecapacity of a lead-acid battery is proportional to the surface area ofthe electrodes that is exposed to the electrolyte, various schemes areemployed to increase the surface area of the electrodes per unit volumeor weight. Plates are grooved or perforated to increase their surfacearea. Faure pasted-plate construction is typical of automotivebatteries. Each plate consists of a rectangular lead grid alloyed withantimony or calcium to improve the mechanical characteristics. Eachplate consists of a rectangular lead grid alloyed with antimony orcalcium to improve the mechanical characteristics.

The holes of the grid are filled with a paste of red lead and 33% dilutesulfuric acid. (Different manufacturers vary the mixture). The paste ispressed into the holes in the grid which are slightly tapered on bothsides to better retain the paste. This porous paste allows the acid toreact with the lead inside the plate, increasing the surface area manyfold. At this stage the positive and negative plates are similar;however expanders and additives vary their internal chemistry to assistin operation.

The present design results in higher energy densities and also lessproblems with the volume changes of the electrodes. The present designresults in more cyclability due to more homogeneous cell design and byputting the positive electrodes parallel to each other and the ground,the active material just transfers from the top layers to the bottomlayers but will not be lost. This also adds to the safety of the cell byreducing the likelihood of shorts.

As an example construction consisting of: Positive electrode: 20 platesof 400×400×5 mm as the grid with holes of 5.5 mm diameter with adistance between the holes of 5 mm, wall to wall; Negative electrodes:rods with diameter of 5 mm. The rods can be placed horizontally;optionally a metal such as steel core is used to support the rodsmechanically.

EXAMPLE 5 Sample Electrochemical Cell

This example describes the use of a LiMn₂O₄ cathode (0.2 mm thick twosided with an aluminum current collector 15 micrometers in between) anda graphite anode (0.2 mm thick two sided with the copper currentcollector 15 micrometers in between) with 1-molar LiClO₄-PC electrolytein the new design as follows.

This design has the same amount of active materials (cathode and anode)comparable to a conventional two parallel plates of anode and cathode;each 48.5 mm×48.5 mm=2350 mm² surface area with 0.1 mm thickness, onesided. This gives 235 mm³ active material volume. In summary, thesurface area is 2350 mm² and the volume is 235 mm³.

This sample electrochemical cell is in the form of a cube with 1 cm³volume. Materials: 40 perforated plates, each 10 mm×10 mm with an arrayof 10×10 holes evenly distributed, of LiMn₂O₄ cathode. Rods of graphite10 mm length and 0.1 mm thick (inner shell) around copper wire of 0.65mm diameter (core). The rods also have a 0.05 mm thick, outer shell,separator, for example PP or PE from Celgard, around them.

The holes in the plates are each 0.95 mm diameter. The distance betweenthe holes, wall to wall, is then 0.05 mm.

The active surface area of the LiMn₂O₄ cathode here then includes: 2350mm² on the surface between the holes (40 two sided perforated plates)AND 2390 mm² on the walls of the holes. This shows that the new designhas 4740 mm² surface area which is about 2 times more surface areacomparing to the conventional to parallel plate design with the sameamount of cathode material.

The active surface area of the graphite anode is 2665 mm² which is stillslightly higher than the conventional design.

This shows that half the material is used for the cathode plate, savingmoney on the most expensive part of the battery, and still reaching thesame energy density from the storage system. As this is only anillustrative example, the following parameters and geometry can beoptimized: number of the holes, number of the plates, and size of theholes. Also note that alternatively this example could utilize graphiteperforated plates and LiMn₂O₄ rods.

EXAMPLE 6 Metal-Air Batteries

Optionally methods are used to accelerate the air flow inside the cell,such as by using pumps. Optionally, the space between the parallelplates is filled by perforated plates, at least on the very top and verybottom layer. For example, this is made of desiccants such as silicagel, activated charcoal, calcium sulfate, calcium chloride,montmorillonite clay, and molecular sieves materials. The material canbe covered in a very thin inert coating such as 0.01 mm PTFE. This helpsto increase the safety, performance and life of Li batteries, especiallyin Li-air batteries. The desiccant layers can be removed and replacedafter they are saturated with water.

Useful battery chemistries for this design include: alkaline battery,Zn—MnO2 primary, Zn—MnO₂ secondary, Zn-Air, Zn—AgO, Ni—Zn, Cd—AgO,Zn—HgO, Cd—HgO Ni—Cd, Ni-Metal Hydride, or Ni—H₂ battery.

Optionally, when using different electrolytes, one between each rod andthe corresponding wall of the holes of the plates and another betweenthe perforated plates, a thin membrane is useful. For example about tensof micrometers thick, between the two electrolyte systems to separatethem, for example when they are both fluid such as liquid, as an examplesimilar to a thin O-ring. Optionally the membrane is used to removeunwanted products from the cell or to add assisting materials to thecell. Examples of removing unwanted products from the cell include somegas phases that happen as the product of the chemistry cell reactions,such as hydrogen gas as for example it happens in Flow batteries or inLead Acid batteries, especially in flooded lead-acid batteries. Themembranes used here optionally are inert materials such as PTFE or PE orother membrane products with desired pore sizes or chemistry or surfacebehavior.

EXAMPLE 7 Zn-Air Battery

This example describes a Zn-Air battery embodiment. Each rod is: a(Ni-mesh carbon-layers) tube comprising a manganese-based catalyzedcarbon layer on a screen of Ni. Electrolyte is KOH, for example, 5M inwater. The anode is a zinc metal, for example with a rough surface suchas from applying sand paper on it, as the perforated plates. The aircathode contains a hydrophobic Teflon layer (inner part of the tube, forexample porous to allow oxygen but stop vapor), a thin Nickel mesh layeracting as a current collector and providing a structural support (middlelayer of the tube), and a carbon catalyst layer (outer part of thetube).

The manganese-based catalyzed carbon layer is, for example 0.5 mm thick.The tube inner radius is, for example, 1 mm. There is a 0.02 mmseparator between each rod and the associated hole. The separator canbe, for example, PVA. The thickness of the Zn plates is, for example, 2mm. The dimensions of the cell are, for example, 1 cm diameter cylinderwith the height of 1 cm.

In this example, there are 4 parallel Zn plates. The distance betweenthe Zn plates is optionally partially filled with electrolyte, here withKOH solution in water and partially with 0.2 mm perforated steel plates,and partially filled with air. A space partially filled with liquidelectrolyte and air helps with the life of the battery.

Optionally, zero space is used between Zn plates and have 5 parallel Znplates, each 2 mm, to resemble one Zn plate of 1 cm thick.

The entire cell is inside a case made of steel and covered by a skinmade of PTFE. The case has openings on two parallel sides, say top andbottom, to allow the air flow. A benefit of the new design is that thetubes are open from both ends so the cell can get more air.

EXAMPLE 8 Zn-Air Battery with Assisted Flow

This example describes a Zn-Air battery with assisted flow. Each rod is:a (Ni-mesh carbon-layers) tube comprising a manganese-based catalyzedcarbon layer on a screen of Ni. The electrolyte is KOH. The anode is azinc metal, for example, with a rough surface, such as from applyingsand paper on it, as the perforated plates. The air cathode contains ahydrophobic Teflon layer (inner part of the tube, for example, porous toallow oxygen but stop vapor), a thin Nickel mesh layer acting as acurrent collector and providing a structural support (middle layer ofthe tube), and a carbon catalyst layer (outer part of the tube).

Here the holes in the plates of metal electrode, for example Znperforated plates, have the same size for each plate but have adifferent size for different plates.

The manganese-based catalyzed carbon layer is 0.5 mm thick. The tubeinner radius is variable, for example linearly varying from 0.5 mm fromone side to 2 mm on the other side. The size of the holes-inner radiuscan be optimized, using fluid mechanics principles based on the densityand temperature and viscosity and other parameters of the flow, forefficient flow of the cathode electrode, here air, through them. Furtherassisted flow can be applied by using pumps, for example, at the twoends of the cell where there is access to air to facilitate the flow ofthe cathode materials, here air.

There is a 0.02 mm separator between each rod and the associated hole.The separator can be for example PVA. The thickness of the Zn plates is,for example, 2 mm. The dimensions of the cell are, for example, 1 cmdiameter cylinder with the height of 1 cm.

In this example, there are 4 parallel Zn plates. The distance betweenthe Zn plates is optionally partially filled with electrolyte, here withKOH solution in water and partially with 0.2 mm perforated steel plates,and partially filled with air. A space partially filled with liquidelectrolyte and air helps with the life of the battery.

Optionally, zero space is used between Zn plates and have 5 parallel Znplates, each 2 mm, to resemble one Zn plate of 1 cm thick.

The entire cell is inside a case made of steel and covered by a skinmade of PTFE. The case has openings on two parallel sides, for example,top and bottom, to allow the air flow.

EXAMPLE 9 Li-Air Battery

This example describes a Li-Air battery. The setup of the cellscomprises metallic lithium as the anode, three membrane laminates (twoPC layers and one LAGP layer), and a cathode. The membrane isPC(BN)/LAGP/PC(BN) with the thickness of 1.5 mm, where each layer of pCis about 200-300 micrometers thick. The plates are 20 mm×20 mm×0.4 mm.The cathode is 25% C* +75% LAGP on Ni mesh tube. The cathode tube has aninner opening of 1 mm diameter. Its thickness is 0.5 mm. C* is 60% PWAactivated carbon+40% Ketjen carbon black.

The air cathode contains a hydrophobic Teflon layer, on the inner size,say 0.01 thick (inner part of the tube is, for example, porous to allowoxygen but stop vapor), a thin Nickel mesh layer acting as a currentcollector and providing a structural support (middle layer of the tube),and a carbon catalyst layer (outer part of the tube).

The cell comprises 4 parallel Li perforated plates. The distance betweenthe plates is optionally partially filled with liquid nonaquouselectrolyte, for example, 1M LiPFe/PC/EC/DMC (1:1:3) and partially with0.2 mm perforated steel plates, and partially can be filled with dryoxygen.

Optionally, zero space is used between plates and there are 5 parallelplates, each 0.4 mm, to resemble one plate of 1 mm thick.

The entire cell can is inside a case made of steel and covered by a skinmade of PTFE. The case has openings on two parallel sides, top andbottom, to allow the air flow.

As a note, the concepts of assisted flow, varying hole-sizes and pumps,as described in the flow assisted Zn-Air battery in the above example,are useful with Li-Air batteries of this example as well.

EXAMPLE 10 Flow Batteries

This example describes flow batteries. Useful electrodes for flowbatteries include, but are not limited to: Vanadium, Bromine, Iron,H₂-Zinc, Cerium, B₂, Chromium, Polysulfide and any combination of these.

Two electrolytes are used, one surrounding the anode and one surroundingthe cathode. Useful electrolytes include, but are not limited to, H₂SO₄,VCI₃—HCl, NaBr—HCl, NaS₂, NaBr, HCl, Polymer Electrolyte Membrane-HBR,ZnBr₂, CH₃SO₃H and any combination of these.

A redox flow battery with a stack of perforated cells and a group ofrods (arbitrary aspect ratio; from one that is a circle cross section toa very large number that is a rectangular cross section; thecross-section itself can vary for example in size), with anolyte andcatholyte compartments divided from each other by an ionically selectiveand conductive separator and having respective electrodes. The batteryhas anolyte and catholyte tanks, with respective pumps and a pipework.In use, the pumps circulate the electrolytes to and from the tanks, tothe compartments and back to the tanks. Electricity flows to a load. Theelectrolyte lines are provided with tappings via which fresh electrolytecan be added and further tappings via which spent electrolyte can bewithdrawn, the respective tappings being for anolyte and catholyte. Onrecharging, typically via a coupling for lines to all the tappings, aremote pump pumps fresh anolyte and fresh catholyte from remote storagesand draws spent electrolyte to other remote storages.

In an embodiment, the cell comprises: an anode in a catholytecompartment, a cathode in an anolyte compartment and, an ion selectivemembrane separator between the compartments, a pair of electrolytereservoirs, one for anolyte and the other for catholyte, and electrolytesupply means for circulating anolyte from its reservoir, to the anolytecompartment in the cell and back to its reservoir and like circulatingmeans for catholyte; the battery comprising: connections to itselectrolyte reservoirs and/or its electrolyte supply means so that thebattery can be recharged by withdrawing spent electrolyte and replacingit with fresh electrolyte,

In this design, the electrolyte divider or membrane is optionally adiaphragm between each rod and the walls of the corresponding holes. Itoptionally is a thin tube shape that the inner and outer radii arechosen to fit between the rod and the corresponding wall and is as longas each of the rods or it can be a thin tube shape as long as thethickness of each of the perforated plates.

EXAMPLE 11 Flow Battery First Example

This example describes a flow battery embodiment. Electrolyte 1 and 2are the same in this example: between rods and walls of the holes andbetween the plates: 2M VOSO₄ in 2M H₂SO₄. Temperature: 25 Celsius.

Negative Electrode: Graphite rods, 100 mm long, 1 mm thick on a copperwire of 1 mm diameter. The wires are held in tension from the top andbottom outside of the cell, so that they stay straight. Electrolyte1runs from the outside of the cell into the cell from one end, from theholes between the rods and the walls of the holes in plates; and exitsfrom the opposite end. A pumping system is optionally used to flow theelectrolyte 1.

Positive Electrode: 10 Platinized titanium Perforated Plates which are100×100×3 mm. The holes are periodic in the plane, 5 mm diameter, and 5mm wall to wall. There is a 5 mm distance between the perforated plates.The Electrolyte 2 flows from outside of the cell into the cell throughthis space and exits from the opposite end. A pumping system isoptionally used to flow the electrolyte 2.

The membrane is CMV polystryne sulphoric acid cation-selective typemembrane and is placed next-to the walls of the plates. It is in theform of a thin tube with outer radius of 5 mm and thickness of 0.02 mm.

EXAMPLE 12 Flow Battery Second Example

This example describes a flow battery embodiment.

Electrolyte 1 and 2 are: between rods and walls of the holes. Thepositive electrolyte 0.8 mol dm-3 Ce(III) methanesulfonate in 4.0 moldm-3 methanesulfonic acid. The negative electrolyte compartment contains1.5 mol dm-3 Zn(II) methanesulfonate in 1.0 mol dm-3 methanesulfonicacid.

The electrolytes are circulated through the cell at 4 cm/s using twoperistaltic pumps with high-pressure tubings (Cole-Parmer, 6 mm innerdiameter) on one face of the cell.

The electrolytes (200 cm³ each) are contained in separate tanks.

Carbon polyvinyl-ester composite is used as the negative electrode.

Platinised titanium mesh (70 g Pt/m² loading) is used as the positiveelectrode.

Negative Electrodes are 3 mm diameter rods 100 mm long: 1 mm thicknegative electrode material (here Carbon polyvinyl-ester) shell on acopper wire of 1 mm diameter. The wires are held in tension from the topand bottom, outside of the cell, so that they stay straight.

Positive Electrode: 10 Platinized titanium Perforated Plates which are100×100×4 mm. The holes are periodic in the plane, 10 mm diameter, and10 mm wall to wall. 5% of the space between each two parallel plates isfilled with spacers, the same material as the plates, 5 mm thick and afew millimeters surface area with an arbitrary shape such as cube orcylinder, and in a periodic arrangement. The rest is filled withnegative electrolyte.

The membrane is CMV polystryne sulphoric acid cation-selective typemembrane and is placed next-to the walls of the plates. It is in theform of a thin tube with outer radius of 5 mm and thickness of 0.02 mm.The membrane is also 100 mm long.

Positive electrolyte enters from one face of the cell, flows in theholes between the rods and the walls of the holes in plates; and exitsfrom the opposite end. Positive electrolyte enters from one face of thecell, runs parallel to the plane of the plates, and exits from theopposite face. The rods and the walls of the holes are separated by themembrane sandwiched between two silicone gaskets. Gaskets are tubes each100 mm long, each about 1 mm thick. The inner gaskets have an innerdiameter of 6 mm (that is a 1.5 mm thick shell is left for the flow ofthe positive electrolyte). The outer gaskets have an outer diameter of10 mm. Inner gaskets have large openings in vicinity of the walls of theplates-holes their cylindrical cross section has at least 80% opening,but has less opening between the parallel plates. Outer gaskets havelarge openings, at least 80%, everywhere.

From outer to inner, the construction of the rod is as follows: Siliconegasket (8.04 mm inner diameter, 10 mm outer diameter) (separator) :Membrane (8 mm inner diameter, 8.04 mm outer diameter) : Silicone gasket(6 mm inner diameter, 8 mm outer) (separator) : Negative electrode rod(Carbon polyvinyl-ester 1 mm thick) and Copper wire (3 mm diameter) :Copper wire (1 mm diameter)(current collector).

EXAMPLE 13 Fuel Cells

The three dimensional electrode design is applied to alkaline fuel cell(AFC), polymeric-electrolyte-membrane fuel cell (PEMFC) andphosphoric-acid fuel cell (PAFC) and molten-carbonate fuel cells (MCFCs)and solid-oxide fuel cells (SOFCs).

In some fuel cells or metal air batteries, a major advantage of the newdesign is the ease of CO₂ recirculation from the anode exhaust to thecathode input, especially as needed in molten-carbonate fuel cells. Thisis achieved by using a specific membrane between the two spaces: thespace between the rods and the walls of the holes and the space betweenthe parallel plates.

In some fuel cells or metal air batteries, another advantage is theremoval of adsorbed CO species, especially inpolymeric-electrolyte-membrane fuel cell and more specifically forreformate electrodes as well as for methanol oxidation. This is achievedby using a specific membrane between the two spaces: the space betweenthe rods and the walls of the holes and the space between the parallelplates.

An advantage of the new design is that bipolar plates that are a must inconventional fuel cells (and have corrosion problems if not made ofexpensive materials) are optionally omitted from the new design. In thenew design, due to the truly 3 dimensional design, the bipolar platesare optionally placed on the faces of the cell, not inside the cell.This helps with the life and cost of the fuel cell, providing a majoradvantage as in the new design the current collectors can be in themiddle of the plates and rods, thus they are not in contact with theelectrolyte. The current collectors also optionally give the desiredstructural strength to the cell; this is in addition to the structuralintegrity due to the packed system of tight contacts between the rodsand the walls of the holes.

A major benefit of the new design is that it can handle the thermalshocks, especially those in Fuel cells, much better compared to theconventional systems. This adds to the life of the system.

Besides hydrogen, it is also able to run on biogas (which delivers themost energy per hectare of crops), natural gas, propane, ethanol, dieselor biodiesel. This is because of the ability of the added ability offuel dissociation in the cell due to the new design.

In a typical planar fuel cell design, if an individual cell plate fails,replacement of the cell plate is difficult due to permanent nature ofthe interconnections between the cells and the bipolar interconnectswithin the stack. Therefore an entire substack consisting of amultiplicity of cell plates and associated non-cell components mustnormally be replaced. A fuel cell stack design wherein thecell-containing packets themselves could be replaced, with only aminimum exchange of non-cell components, would offer a significanteconomic advantage.

One advantage of the new design is that the gas and liquid phases of theproducts of the reaction are separable by adding membranes (permeable togas but not to liquid; for example, using PP or PE or other inertmaterials with desired pore sizes) between the rods and the plates atthe levels of beginning and end of the plates. That is the distancebetween the membranes is equal to the thickness of the perforated platesand the membrane can be like a thin donut of say 0.01 mm thick and widthof about a few micrometer to a few millimeters (to fill the spacebetween the rods and the plates). This is very useful as an example forhydrogen and bromine flow battery in which removing the bromine gas inconventional design is difficult. In the new design the gas diffuses tothe space between the plates, where it can be solved in a liquid orpartially mixed with another gas and be removed from the cell, wither bydiffusing out of the system or by assisted flow, say by a pump.

The electrolyte is optionally Aqueous alkaline solution or Aqueousalkaline solution, Polymer membrane (ionomer), Polymer membrane or humicacid, Molten phosphoric acid (H3PO4) or Molten alkaline carbonate orO2—conducting ceramic oxide or salt water or H+-conducting ceramic oxideor yttria-stabilized zirconia (YSZ) or lithium potassium carbonate saltor Ceria.

In general, the electrolyte sheets employed for the construction ofcompliant multi-cell-sheet structures are maintained below 45 microns inthickness, preferably below 30 microns in thickness, and most preferablyin the range of 5-20 microns in thickness. Flexible polycrystallineceramic electrolyte sheets enhance both thermal shock resistance andelectrochemical performance; examples of such sheets are disclosed inU.S. Pat. No. 5,089,455 to Ketcham et al.,hereby incorporated byreference. Examples of suitable compositions for such electrolytesinclude partially stabilized zirconias or stabilized zirconias dopedwith a stabilizing additive selected from the group consisting of theoxides of Y, Ce, Ca, Mg, Sc, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu,In, Ti, Sn, Nb, Ta, Mo, and W and mixtures thereof.

Among the electrode materials useful in combination with pre-sinteredelectrolytes are cermet materials such as nickel/yttria stabilizedzirconia cermets, noble metal/yttria stabilized zirconia cermets, thesebeing particularly useful, but not being limited to use, as anodematerials. Useful cathode materials include such ceramic and cermetmaterials as strontium-doped lanthanum manganite, other alkalineearth-doped cobaltites and manganites as well as noble metal/yttriastabilized zirconia cermets. Of course the foregoing examples are merelyillustrative of the various electrode and interconnect materials whichare useful and are not intended as limiting.

Cathode and anode materials useful for fuel cell construction preferablycomprise highly conductive but relatively refractory metal alloys, suchas noble metals and alloys amongst and between the noble metals, e.g.,silver alloys. Examples of specific alloy electrode compositions of thistype include silver alloys selected from the group consisting of silverpalladium, silver-platinum, silver-gold and silver-nickel, with the mostpreferred alloy being a silver-palladium alloy. Alternative electrodematerials include cermet electrodes formed of blends of these metals ormetal alloys with a polycrystalline ceramic filler phase. Preferredpolycrystalline ceramic fillers for this use include stabilizedzirconia, partially stabilized zirconia, stabilized hafnia, partiallystabilized hafnia, mixtures of zirconia and hafnia, ceria with zirconia,bismuth with zirconia, gadolinium, and germamum. In addition, Grapheneis optionally used as either of the electrodes.

The three most common electrolyte materials in SOFCs are: doped ceria(CeO2), doped lanthanum gallate (LaGaO3) (both are oxygen ionconductors) and doped barium zirconate (BaZrO3) (a proton conductor).

In fuel cells the anode is usually hydrogen or hydrocarbon fuels,including diesel, methanol and chemical hydrides.

The membrane is optionally Nafion or Polyarylenes or polybenzimidazole(PBI) with phosphoric acid.

Conventional fuel cells in general have slow reaction rates, leading tolow currents and power. The new design makes the reaction rate muchfaster by increasing the active surface area and also by bettermanagement of the flow of the reaction products, and also by making thecell more homogeneous.

EXAMPLE 14 SOFC Fuel Cell

This example describes a single oxide fuel cell operating at atemperature of up to 700 degrees Celsius. Geometry: Here rods are hollowand have a square cross section. Each rod is 100 mm long, and has anouter size of 14.95 mm×14.95 mm. The outer layer of each rod is cathodeactive material (Doped LaMnO₃) 0.2 mm thick with low porosity and smallmean pore diameter (1 μm or less). The inner layer is a 1 mm thicksupport material with higher porosity and larger mean pore diameter (2μm or more).

Electrolyte is solid thin tubes, 100 m long, with 0.05 mm thickness. Therods are coated with the electrolyte which fills the space between therods and the walls of the holes of the plates. The Electrolyte materialis YSZ.

The plates are 2 mm thick. They have a 1.8 mm steel in the center with0.1 mm thick coating on each side made of the anode material (Ni/YSZ).They are 100 mm×100 mm wide-long. They have square holes of 15 mm×15 mmsize. The holes are distributed periodically. The least distance betweenthe holes is 10 mm wall to wall. The distance between parallel plates is10 mm.

The fuel flows in the space between the plates. The oxidizing fluid,such as oxygen gas, flows in the inner space of the hollow rods.

EXAMPLE 15 Supercapacitor, First Example

This example describes an electrochemical supercapacitor. The geometryof the device is a box of 1×1×1 cm. In this example, the rod electrodesare 0.02 mm diameter and are 10 mm long. There are 10 parallel plateelectrodes, each 10×10×0.02 mm. The plate electrodes have periodic holesof 0.03 mm diameter and the distance between the holes is 0.02 mm wallto wall. The distance between parallel plates is 0.08 mm. The spacebetween the parallel plates and between each rod and the correspondingwalls of the holes is filled with the electrolyte.

All rods have a 0.01 mm diameter copper core. The active material is theshell such that: half of the rods are made of MnO₂, the other half aremade of activated Carbon. They are assembled next to each other: eachMnO₂ rod has four nearest neighbors of Carbon; and each carbon has fournearest neighbors of MnO2.

All plates have a 0.01 mm thick copper core. The active material is theshell such that: half of the plates are made of activated Carbon. Theother half are made of MnO₂. Each Carbon plate has two MnO₂ neighbors(top and bottom), and each MnO₂ plate has two carbon plate neighbors.

The electrolyte is 0.5M H₂SO₄ in water. The rods are positively chargedand the plates are negatively charged.

A fuel flows in the space between the plates. The oxidizing fluid, suchas an oxygen containing gas, flows in an inner space of the hollow odeelectrodes.

EXAMPLE 16 Supercapacitor, Second Example

This example describes a supercapacitor. The geometry is a box of 1×1×1cm. In this example, the rods electrodes are 0.02 mm diameter and are 10mm long. The plate electrodes are 10×10×0.02 mm, and have periodic holesof 0.03 mm diameter. The distance between the holes is 0.02 mm wall towall. The distance between parallel plates is 0.08 mm. There are 10parallel plates. The space between the parallel plates and between eachrod and the corresponding walls of the holes is filled with theelectrolyte. In this example, the electrolyte is 1 M LiClO₄ in PropyleneCarbonate.

All rods have a 0.01 mm diameter copper core. The active material is theshell such that: half of the rods are made of MnO₂, the other half aremade of activated Carbon. They are assembled next to each other: eachMnO₂ rod has four nearest neighbors of Carbon; and each carbon has fournearest neighbors of MnO₂.

All plates have a 0.01 mm thick copper core. The active material is theshell such that: half of the plates are made of activated Carbon. Theother half are made of MnO₂. Each Carbon plate has two MnO₂ neighbors(top and bottom), and each MnO₂ plate has two carbon plate neighbors.

The MnO₂ rods and plates are positively charged and the Carbon rods andrelates are negatively charged.

The MnO₂ rods and plates are positively charged from bottom and left ofthe cell and the Carbon rods and plates are negatively charged from topand right side of the cell.

EXAMPLE 17 Supercapacitor, Third Example

This example describes a small design supercapacitor. The geometry ofthe device is a box of 0.1×0.1×0.1 mm inside size. The rod electrodesare 0.01 mm diameter. They are 0.1 mm long. The plates electrodes are0.1×0.1×0.005 mm, and have periodic holes of 0.015 mm diameter, thedistance between the holes is 0.01 mm wall to wall. The distance betweenparallel plates is 0.005 mm. There are 10 parallel plates. The spacebetween the parallel plates and between each rod and the correspondingwalls of the holes is filled with the electrolyte. The electrolyte inthis example is 1 M LiClO₄ in Propylene Carbonate.

Half of the rods are made of MnO₂, the other half are made of activatedCarbon. They are assembled next to each other: each MnO₂ rod has fournearest neighbors of Carbon; and each carbon has four nearest neighborsof MnO₂.

Half of the plates are made of activated Carbon. The other half are madeof MnO₂. Each Carbon plate has two MnO₂ neighbors (top and bottom), andeach MnO₂ plate has two carbon plate neighbors.

The MnO₂ rods and plates are positively charged and the Carbon rods andplates are negatively charged.

EXAMPLE 18 Half Semi-Solid Battery

This example describes a semi-solid battery. The geometry of the deviceis a box of 100×100×100 mm inside size. The rod electrodes are 5 mm indiameter and are 100 mm long. The plate electrodes are 100×100×2 mm, andhave periodic holes of 6 mm diameter; the distance between the holes is2 mm wall to wall. The distance between parallel plates is 0.5 mm. Thereare 40 parallel plates in this example.

The space between the parallel plates and between each rod and thecorresponding walls of the holes is filled with the electrolyte andcathode particles. Electrolyte and cathode particles enter from outsideof the cell though the open spaces between the rods and the walls of theholes in the plates and also between the plates. One or several pumpscan be used for this purpose.

Cathode particles are LiCoO₂ powder (nanometer size to micrometer size)mixed with carbon black powders (nanometer size to micrometer size), 90%to 10% weight. The electrolyte is 1 M LiPF₆ in alkyl carbonate blend.

The rods are made of copper. The plates are made of three silicon(anode) layers that are separated by two perforated copper plates, 0.010mm thick. The distance between the copper plates is 1 mm.

The surfaces, including edges of the walls of the holes, of the platesare covered with an inert micro-porous material as a coating, here 0.1mm PE separator.

EXAMPLE 19 Full Semi-Solid Battery

This example describes a semi-solid battery. The geometry of the deviceis a box of 100×100×100 mm inside size. The rod electrodes are 5 mm indiameter and are 100 mm long.

Plates are 100×100×2 mm, and have periodic holes of 6 mm diameter; thedistance between the holes is 2 mm wall to wall. The distance betweenparallel plates is 0.5 mm. There are 40 parallel plates in this example.

The space between the parallel plates and between each rod and thecorresponding walls of the holes is filled with the electrolyte andcathode particles.

Electrolyte 1 and cathode particles enter from outside of the cellthough the open spaces between the rods and the walls of the holes inthe plates.

Electrolyte 2 and anode particles enter from outside of the cell thoughthe open spaces between the plates. One or several pumps can be used forthis purpose.

Cathode particles are LiFePO₄ powder (nanometer size to micrometer size)mixed with carbon black powders (nanometer size to micrometer size), 90%to 10% weight.

Electrolyte 1 is 1 M LiPF₆ in alkyl carbonate blend.

Anode particles are Li₄Ti₅O₁₂ powder (nanometer size to micrometer size)mixed with carbon black powders (nanometer size to micrometer size), 90%to 10% weight.

Electrolyte 2 is 70:30 (weight) 1,3-dioxolane and LiBETI.

The rods are made of copper and the plates are made of copper.

Between each of the rods and the walls of the holes of the plates thereis a tube of PE separator, 0.05 mm thick, same length as the rods, 100mm, with external diameter of 6 mm.

To construct an electrode array of this design, the tubes are placedafter all the plates are aligned and before the rods are placed throughthe holes. Then the tubes are inflated by introducing a fluid, such ashexane or the cathode electrolyte, into them through both ends (or fromone end while the other end is kept closed) while the tube is in tensionfrom both ends from the outside.) Optionally, a balloon can be placedinside the tube to help with the inflation, this works as by inflatingthe balloon the tube is sealed to the walls of the holes of the plates.The balloon is removed after the inert tube is fit with the walls of theholes. Optionally, all the plates are attached to each other first, thenthe tube is inflated and the distance between the plates is adjustedwhile still inflating the tubes with either of the above methods.

EXAMPLE 20 Small Semi-Solid Battery

This example describes a small/nano scale battery. The geometry of thedevice is a box of 0.01×0.01×0.01 mm inside size. The rod electrodes are0.001 mm in diameter and are 0.01 mm long. The plate electrodes are0.01×0.01×0.0005 mm, and have periodic holes 0.0015 mm in diameter,where the distance between the holes is 0.001 mm wall to wall. Thedistance between parallel plates is 0.0005 mm. There are 10 parallelplates in this example.

The space between the parallel plates and between each rod and thecorresponding walls of the holes is filled with the electrolyte. Here,the electrolyte is 1 M LiClO₄ in Propylene Carbonate.

The rods are made of LiCoO₂ and the plates are made of silicon.

EXAMPLE 21 Composite Rod Electrode

This example describes a rod electrode that is a composite electrodeitself. For example, in reference to the embodiment shown in FIG. 14, arod electrode has a core of current collector material such as aluminum.Surrounding the current collector is a layer of LiCoO₂, for example, 0.1mm thick. Surrounding the LiCoO₂ layer, then there is a layer of PE orPP or Celgard, for example 0.2 mm thick. Surrounding this layer is alayer of Si, for example, 0.10 mm thick. Surrounding the Si layer is asecond current collector, a layer of, for example, 0. 01 mm copper.Surrounding the second current collector is a layer of Si, for example,0.01 mm thick.

In this example, a three-dimensional electrode array comprises 30parallel plates of LiCoO₂, each 0.2 mm thick (optionally having a 0.01mm thick Al current collector in the middle), and 7.5 mm×7.5 mm long andwide.

The footprint area of this example is more than 41 times smaller than aconventional design, which makes it an ideal case for small electronic,MEMS, and biomedical devices.

The volume of the design in this example is about 0.67 of that of theconventional design, much smaller than the conventional design.

The surface areas of the plate and rod electrodes are respectively, 1.52and 1.02 times increased from the conventional design.

REFERENCES

U.S. Pat. Nos. 7,553,584, 528,647, 3,168,458, 4,346,152, 4,871,428,4,981,672, 6,781,817, 7,618,748, 5,089,455, 5,510,209, 4,786,567,4,041,211.

US Patent Application Publications US 2011/0171518, US 2003/0099884, US2005/0095504, US 2002/0160263, US 2004/0018431, US 2004/0175626, US2004/0241540, US 2005/0074671, US 2007/0059584, US 2008/0153000, US2009/0035664, US 2009/0087730, US 2009/0197170, US 2009/0214956, US2011/0104521, US 2003/0096147, US 2007/0117000, US 2010/0047671.

International Patent Application Publications WO 2008/019398, WO2010/0057579, WO 1997/006569, WO 2008/049040, WO 2008/153749, WO2010/062391.

http://www.liquicel.com/uploads/documents/Membrane%20Contactors%20-%20An%20Introduction%20To%20The%20Technology.pdf

Journal of The Electrochemical Society, 157, 1, A50-A54 (2010).

STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS

All references throughout this application, for example patent documentsincluding issued or granted patents or equivalents; patent applicationpublications; and non-patent literature documents or other sourcematerial; are hereby incorporated by reference herein in theirentireties, as though individually incorporated by reference, to theextent each reference is at least partially not inconsistent with thedisclosure in this application (for example, a reference that ispartially inconsistent is incorporated by reference except for thepartially inconsistent portion of the reference).

All patents and publications mentioned in the specification areindicative of the levels of skill of those skilled in the art to whichthe invention pertains. References cited herein are incorporated byreference herein in their entirety to indicate the state of the art, insome cases as of their filing date, and it is intended that thisinformation can be employed herein, if needed, to exclude (for example,to disclaim) specific embodiments that are in the prior art. Forexample, when a compound is claimed, it should be understood thatcompounds known in the prior art, including certain compounds disclosedin the references disclosed herein (particularly in referenced patentdocuments), are not intended to be included in the claim.

When a group of substituents is disclosed herein, it is understood thatall individual members of those groups and all subgroups and classesthat can be formed using the substituents are disclosed separately. Whena Markush group or other grouping is used herein, all individual membersof the group and all combinations and subcombinations possible of thegroup are intended to be individually included in the disclosure. Asused herein, “and/or” means that one, all, or any combination of itemsin a list separated by “and/or” are included in the list; for example“1, 2 and/or 3” is equivalent to “‘1’ or ‘2’ or ‘3’ or ‘1 and 2’ or ‘1and 3’ or ‘2 and 3’ or ‘1, 2 and 3’”.

Every formulation or combination of components described or exemplifiedcan be used to practice the invention, unless otherwise stated. Specificnames of materials are intended to be exemplary, as it is known that oneof ordinary skill in the art can name the same material differently. Oneof ordinary skill in the art will appreciate that methods, deviceelements, starting materials, and synthetic methods other than thosespecifically exemplified can be employed in the practice of theinvention without resort to undue experimentation. All art-knownfunctional equivalents, of any such methods, device elements, startingmaterials, and synthetic methods are intended to be included in thisinvention. Whenever a range is given in the specification, for example,a temperature range, a time range, or a composition range, allintermediate ranges and subranges, as well as all individual valuesincluded in the ranges given are intended to be included in thedisclosure.

As used herein, “comprising” is synonymous with “including,”“containing,” or “characterized by,” and is inclusive or open-ended anddoes not exclude additional, unrecited elements or method steps. As usedherein, “consisting of” excludes any element, step, or ingredient notspecified in the claim element. As used herein, “consisting essentiallyof” does not exclude materials or steps that do not materially affectthe basic and novel characteristics of the claim. Any recitation hereinof the term “comprising”, particularly in a description of components ofa composition or in a description of elements of a device, is understoodto encompass those compositions and methods consisting essentially ofand consisting of the recited components or elements. The inventionillustratively described herein suitably may be practiced in the absenceof any element or elements, limitation or limitations which is notspecifically disclosed herein.

The terms and expressions which have been employed are used as terms ofdescription and not of limitation, and there is no intention in the useof such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theinvention claimed. Thus, it should be understood that although thepresent invention has been specifically disclosed by preferredembodiments and optional features, modification and variation of theconcepts herein disclosed may be resorted to by those skilled in theart, and that such modifications and variations are considered to bewithin the scope of this invention as defined by the appended claims.

1.-28. (canceled)
 29. A method of controlling a temperature of anelectrochemical cell, the method comprising the steps of: providing anelectrochemical cell comprising: a plurality of plate electrodes,wherein each plate electrode includes an array of apertures, wherein theplate electrodes are arranged in a substantially parallel orientationsuch that tho each aperture of an individual plate electrode is alignedalong an alignment axis passing through an aperture of each of all otherplate electrodes; and a plurality of rod electrodes, wherein theplurality of rod electrode are not in physical contact with theplurality of plate electrodes and arranged such that each rod electrodeextends a length along an alignment axis passing through an aperture ofeach plate electrode; wherein a first surface area includes a cumulativesurface area the plurality of plate electrodes, wherein a second surfacearea includes a cumulative surface area of each aperture array andwherein a third surface area includes a cumulative surface area of eachof the plurality of rod electrodes; wherein each of the plurality ofplate electrodes comprises a current collector, wherein each of theplurality of rod electrodes comprises a current collector or whereineach of the plurality of plate electrodes comprises a current collectorand each of the plurality of rod electrodes comprises a currentcollector; and positioning one or more of the current collectors inthermal communication with a heat sink or a heat source.
 30. A method ofcontrolling a temperature of an electrochemical cell, the methodcomprising the steps of: providing an electrochemical cell comprising: aplurality of plate electrodes, wherein each plate electrode includes anarray of apertures, wherein the plate electrodes are arranged in asubstantially parallel orientation such that tho each aperture of anindividual plate electrode is aligned along an alignment axis passingthrough an aperture of each of all other plate electrodes; and aplurality of rod electrodes, wherein the plurality of rod electrode arenot in physical contact with the plurality of plate electrodes andarranged such that each rod electrode extends a length along analignment axis passing through an aperture of each plate electrode; oneor more heat transfer rods arranged such that each heat transfer rodextends a length along an alignment axis passing through an aperture ofeach plate electrode; wherein a first surface area includes a cumulativesurface area the plurality of plate electrodes, wherein a second surfacearea includes a cumulative surface area of each aperture array andwherein a third surface area includes a cumulative surface area of eachof the plurality of rod electrodes; wherein each of the plurality ofplate electrodes comprises a current collector, wherein each of theplurality of rod electrodes comprises a current collector or whereineach of the plurality of plate electrodes comprises a current collectorand each of the plurality of rod electrodes comprises a currentcollector; and positioning one or more of the heat transfer rods inthermal communication with a heat sink or a heat source.
 31. (canceled)32. A redox flow energy storage device comprising: a first electrodecurrent collector in the form of a rods, a second electrode currentcollector in the form of a grid or a grating of crossed bars, and anion-permeable membrane separating said positive and negative currentcollectors; a first electrode disposed between the first electrodecurrent collector and the ion-permeable membrane; the first electrodecurrent collector and the ion-permeable membrane defining a firstelectroactive zone accommodating the first electrode; a second electrodedisposed between the second electrode current collector and theion-permeable membrane; the second electrode current collector and theion-permeable membrane defining a second electroactive zoneaccommodating the negative electrode; wherein at least one of the firstand second electrode comprises a flowable semi-solid or condensed liquidion-storing redox composition capable of taking up or releasing ionsduring operation of the cell; and wherein the first electrode is apositive electrode, the first current collector is a positive electrodecurrent collector, the first electroactive zone is a positiveelectroactive zone, the second electrode is a negative electrode, thesecond current collector is a negative electrode current collector, andthe second electroactive zone is a negative electroactive zone; orwherein the first electrode is a negative electrode, the first currentcollector is a negative electrode current collector, the firstelectroactive zone is a negative electroactive zone, the secondelectrode is a positive electrode, the second current collector is apositive electrode current collector, and the second electroactive zoneis a positive electroactive zone.
 33. A method of operating a redox flowenergy storage device, comprising the steps of: providing a redox flowenergy storage device of claim 32; and transporting the flowablesemi-solid or condensed liquid ion-storing redox composition into theelectroactive zone during operation of the device.
 34. A redox flowbattery comprising a stack of perforated plate electrodes and a group ofrod electrodes, wherein each rod electrode passes through an aperture ofeach plate electrode, and anolyte and catholyte compartments dividedfrom each other by an ionically selective and conductive separator andhaving respective electrodes; and anolyte and catholyte tanks, withrespective pumps and pipeworks to provide fluid communication betweenthe respective anolyte and catholyte tanks and compartments; and whereinthe pumps circulate the electrolytes to and from the tanks, to thecompartments and back to the tanks, and wherein electricity flows to aload; and wherein the electrolyte lines are provided with tappings viawhich fresh electrolyte can be added and further tappings via whichspent electrolyte can be withdrawn, the respective tappings being foranolyte and catholyte; and wherein, on recharging, via a coupling forlines to all the tappings, a remote pump pumps fresh anolyte and freshcatholyte from remote storages and draws spent electrolyte to otherremote storages.